Corentin Bochaton
email: corentin.bochaton@u-bordeaux.fr

Brice Ephrem

Benoît Bérard

David Cochard

Monica Gala

Kristine Korzow Richter

Alice Le Lay

Sylvain Renou

Arnaud Lenoble

Benoit Bérard

Kristine Korzow Richter

The pre-Columbian site of Roseau

Keywords: Amerindian, Caribbean, Island, Subsistence, Tropics, Zooarchaeology Declarations

published or not. The documents may come

Introduction

Subsistence strategies of archaeological populations reflect the complex interaction between environmental pressures, demographic contexts, and cultural choices of human groups [START_REF] Politis | Archaeological Correlates of Ideological Activity: Food Taboos and Spiritanimals in an Amazonian Hunter-gatherer Society[END_REF]. However, it is often challenging to separate the influence of different factors on choices made by humans when exploiting the resources in a specific environment, as it requires a good understanding of the contemporaneous natural environments and socio-economic characteristics of archaeological populations. Insular contexts represent a good opportunity for such studies as they provide a context where it is easier to evaluate the availability of the limited resources accessible to human groups and the corresponding cultural choices. The Caribbean islands have been the objects of numerous zooarchaeological studies but extensive data are still only available on a limited sample of islands (e. g. deFrance, 1990;[START_REF] Newsom | On Land and Sea: Native American Uses of Biological Resources in the West Indies[END_REF][START_REF] Grouard | Modes de vie des Précolombiens des Antilles françaises[END_REF][START_REF] Lefebvre | The Zooarchaeology of Islands: Towards Synergy and Synthesis[END_REF]. Currently available data have permitted the proposal of diverse hypotheses regarding the subsistence behaviors of the successive Amerindian inhabitants of the Caribbean Lesser Antilles. However, as research grows in this region more evidence emerges of chronological and geographical variability in human subsistence behaviors.

The first human populations to colonize these islands (between 5800 and 2500 cal years B.P. (Archaic Age)) were non-ceramic populations [START_REF] Siegel | Paleoenvironmental evidence for first human colonization of the eastern Caribbean[END_REF][START_REF] Bérard | About Boxes and Labels: A Periodization of the Amerindian Occupation of the West Indies[END_REF][START_REF] Napolitano | Reevaluating human colonization of the Caribbean using chronometric hygiene and Bayesian modeling[END_REF]. They were later replaced around ca. 400 BC by ceramic populations originating from South America the first of which (Early and Middle Ceramic) are from the Saladoid cultural current (see [START_REF] Bérard | About Boxes and Labels: A Periodization of the Amerindian Occupation of the West Indies[END_REF] for more detailed subdivisions). Although we now have archaeological evidence that these Amerindian populations occupied nearly all of the Lesser Antillean islands, the general colonization pattern is subject to much chronological variability at the regional scale [START_REF] Giovas | Prehistoric migration in the Caribbean: past perspectives, new models and the ideal free distribution of West Indian colonization[END_REF]. Differences on size and geology between islands create a diversity of natural habitats and resources at an inter-island level which allows for the study of Amerindians subsistence behaviors in different geographical, ecological, and chronological contexts.

Several studies have tried to approach these questions and to establish regional models regarding Amerindian exploitation of their environment in the Lesser Antilles. The first regional zooarchaeological studies initially observed a shift from terrestrial to aquatic resources during the Ceramic period. This was first explained as population replacement where Early Ceramic populations that consumed terrestrial crabs were replaced by later populations that consumed marine shellfish [START_REF] Rainey | Scientific Survey of Porto Rico and Virgin Islands[END_REF]). Subsequent research identified other possible explanations to explain this shift of subsistence behaviors, including climate change, overexploitation of terrestrial crabs, and diet breadth expansion following population growth [START_REF] Goodwin | The prehistoric cultural ecology of St. Kitts, West Indies: A case study in island archaeology[END_REF][START_REF] Carbone | The paleoecology of the Caribbean area[END_REF][START_REF] Keegan | Transition from a terrestrial to a maritime economy: A new view of the crab/shell dichotomy[END_REF]). More complex hypotheses have also been proposed which integrate cultural choices with island ecology. As the evolution of Amerindian diet from terrestrial to aquatic resources is also observed in vertebrate bone remains, some researchers have proposed that the earlier populations tried to replicate their continental way of life by including a significant amount of terrestrial animals in their diet. In contrast, the populations (see [START_REF] Bérard | About Boxes and Labels: A Periodization of the Amerindian Occupation of the West Indies[END_REF] for details) that occupied the region during the Late and Final Ceramic periods developed strategies that focused primarily on the more plentiful, marine resources [START_REF] Jones | Dietary Change and Human Population at Indian Creek, Antigua[END_REF][START_REF] Wing | Human exploitation of animal resources[END_REF].

A second complex hypothesis for the change in subsistence strategies through time was the exhaustion of natural resources, possibly related to a population increase, that may have forced Amerindians to enlarge their diet breadth [START_REF] Goodwin | The prehistoric cultural ecology of St. Kitts, West Indies: A case study in island archaeology[END_REF][START_REF] Keegan | Transition from a terrestrial to a maritime economy: A new view of the crab/shell dichotomy[END_REF]. This was proposed primarily to explain the simultaneous reduction of the mean trophic level of marine resources and the size of fish consumed during the Late Ceramic period in the Virgin Islands [START_REF] Wing | Prehistoric fisheries in the Caribbean[END_REF] and Bahamas [START_REF] Blick | Pre-Columbian impact on terrestrial, intertidal, and marine resources, San Salvador, Bahamas (A.D. 950-1500)[END_REF]). Although there is a possible global trend for the temporal reduction of the size of archaeological fishes at the regional scale [START_REF] Grouard | Size estimation of pre-Columbian Caribbean fish[END_REF]), the pattern observed on the Virgin Islands and Bahamas has not been observed on other islands, including Carriacou (Giovas 2016a), Guadeloupe (Grouard 2001a), and Anguilla [START_REF] Carder | Fish communities and populations during the post-Saladoid period (AD 600/800-1500), Anguilla, Lesser Antilles[END_REF][START_REF] Allen | Zooarchaeological analysis of fishing at the Rendezvous Bay site, Anguilla: an investigation into possible overexploitation of marine fishes[END_REF][START_REF] Carder | A pre-Columbian fisheries baseline from the Caribbean[END_REF]. As more zooarchaeological studies were conducted, both the regional trends and single explanations for subsistence changes have been called into question. The Ceramic Age subsistence strategies have been found to be highly adaptive and diverse (Wing 2001a;[START_REF] Newsom | On Land and Sea: Native American Uses of Biological Resources in the West Indies[END_REF]. The majority of sites report that the consumption of animal protein by Amerindian groups consisted primarily of aquatic resources, including in Archaic Age deposits (Hofman and Hoogland 1999;[START_REF] Newsom | On Land and Sea: Native American Uses of Biological Resources in the West Indies[END_REF]). This result is in accordance with the richness of the Caribbean coral reefs, and the proximity of most sites to the sea. In addition, some Ceramic Age assemblages deviate from this trend with a notable consumption of terrestrial animals, for instance: Trants in Montserrat [START_REF] Reitz | Archaeology of Trants, Montserrat. Part 2. Vertebrate Fauna[END_REF]), Cayon at St-Kitts [START_REF] Wing | Use of animals by the prehistoric inhabitants of St. Kitts[END_REF], Hope Estate in Saint-Martin [START_REF] Grouard | Variation des stratégies de subsistance des Précolombiens à Hope Estate, Saint-Martin (Petites Antilles), d'après l'analyse des restes des petits vertébrés[END_REF], and Morel in Guadeloupe [START_REF] Grouard | Modes de vie des Précolombiens des Antilles françaises[END_REF]. This absence of archaeological evidence of a chronological evolution from a terrestrial toward a marine diet at the regional scale is also in accordance with isotopic data which suggest that the size and geology of the island (limestone vs. volcanic) has a prominent impact on Amerindian subsistence choices [START_REF] Stokes | A biogeographic survey of prehistoric human diet in the West Indies using stable isotopes[END_REF].

The reasons for the Amerindian variation in subsistence strategy are therefore presently unclear, especially because there is no longer a clear regional chronological change. An intra-site chronological transition from a dominant exploitation of terrestrial to a dominant exploitation of aquatic resources, or the reverse, has only been observed two times in the Lesser Antilles, at the Indian Creek [START_REF] Jones | Dietary Change and Human Population at Indian Creek, Antigua[END_REF], and AR-38/AR-39 [START_REF] Carlson | Examining Temporal Differences in Faunal Exploitation at Two Ceramic Age Sites in Puerto Rico[END_REF] sites. While similar but more subtle subsistence strategies modifications are suggested by the assemblages of Keldey's Ridge site (Wing 2001a), and possibly Sabazan (Giovas 2016b) although the material is not abundant enough to draw a clear conclusion from the latter. This is problematic as the zooarchaeological study of such assemblages is, along with isotopic study of human remains, the only possible way to emphasis a modification in the behavior of a human group that is potentially independent of environmental modification. In this study, we demonstrate and discuss an additional occurrence of an intra-site chronological transition in this case from a primarily aquatic to a primarily terrestrial subsistence strategy in the Late Ceramic assemblage of Roseau in Guadeloupe. The complete profile of the faunal and ceramic assemblage is described, a series of new radio-carbon dates obtained, and a reinterpretation of the stratigraphy of the site is proposed. The interpretation of this transition in light of the dense paleoenvironmental data available in the Guadeloupe islands is further discussed.

The site of Roseau

The Guadeloupe Islands are located in the central part of the Lesser Antilles between Dominica and Montserrat (Fig. 1). The oldest archaeological site in these islands is the site Pointe des Pies dating to around 1000 cal. BC, [START_REF] Richard | Premier indice d'une occupation précéramique en Guadeloupe continentale[END_REF]) but indirect paleoenvironmental evidence indicate that the first human settlements may be as old as 3000 cal. BC [START_REF] Stouvenot | L'abri sous roche Cadet 3 (Marie-Galante): un gisement à accumulations de faune et à vestiges archéologiques[END_REF][START_REF] Siegel | Paleoenvironmental evidence for first human colonization of the eastern Caribbean[END_REF]. The oldest Ceramic Age site is Morel I, an Early Ceramic site (Huecan Saladoid cultural current) dating to around AD 80 [START_REF] Clerc | Le peuplement précolombien des Antilles et ses vestiges en Guadeloupe[END_REF]Hofman et al. 1999). More recent archaeological sites dating from the Early to the Final Ceramic periods are numerous in Guadeloupe [START_REF] Delpuech | Guadeloupe amérindienne[END_REF] but the evidence for Contact period (Cayo cultural current) sites are rare. The Contact period follows the arrival of Columbus in 1493, and ends with the first permanent European settlements in 1635 [START_REF] Keegan | The Oxford Handbook of Caribbean Archaeology[END_REF]. One of the few sites from this brief period is Roseau on Basse-Terre, the largest island of Guadeloupe. Its name refers to the Roseau beach on which it lies, on the southeastern coast of the Island, 1.5 km south of the town of Ste Marie (N16°5 '41.988'',, in an environment of seasonal evergreen forest, around 2 km from the lower edge of the windward rainforest [START_REF] Rousteau | Carte écologique de la Guadeloupe[END_REF].

The site at the beach of Roseau was identified in the 1960s through surface recovery of archaeological remains but was not excavated until 2001 and 2002 by Gérard Richard [START_REF] Richard | Le site archéologique de la plage de Roseau à Capesterre Belle Eau révélateur d'une occupation caraïbe insulaire en Guadeloupe[END_REF]. The nearby site at the parking lot of Roseau situated 200m south of the beach site was more recently excavated by INRAP but did not provide an assemblage of bone comparable to the one recovered from the beach site (van den [START_REF] Van Den Bel | Parking de Roseau: Sainte-Marie avant l'arrivée de Christophe Colomb[END_REF]. The beach excavation involved several trenches; most of the ceramic material and all of the vertebrate remains were collected in trenches B0-B1-B2 and A0-A1 (Fig. 1-b). A sieving column set in the middle of the B0-B1 trench enabled the recovery of most of the faunal remains. The excavated area was identified as a pit in the form of a ravine, filled with a stratified dump, as demonstrated by the stratigraphy of the trench B0-B2 (Fig. 1-b). The excavation consisted of a trench cut into the upstream portion of the ravine, uncovering infilling to a depth of two meters. Three main layers were identified during the excavation (Fig. 2-a).

The first studies identified the cultural and chronological attributions from the ceramic assemblages and C14 dating of unidentified shells and a human bone (see Sup. Mat. 1). Level 1 was assigned to the Contact period from a calibrated date between 1432 and 1502 AD. This level contained some remarkable finds, such as a manatee bone cup carved with a zoomorphic pattern interpreted as being of Taíno origin. Level 2 was identified as Final Ceramic (Suazan Troumassoid cultural current) from a calibrated date between 1274 and 1367 AD, and level 3 was identified as Late Ceramic (Troumassan Troumassoid cultural current) from a calibrated date between 997 and 1090 AD. The surface finds were attributed to a hypothetical level called "0". However, more recent reconsideration of these chronostratigraphic assignations have revealed them to be somewhat artificial. Contextual information from dated samples in the Banadora database (http://www.arar.mom.fr/banadora) indicate that the C14 dating of level 1 was obtained from a surface remain and that the date for level 3 comes from a bone collected in level 2. In addition, other unpublished dates were obtained immediately following the excavation, and potentially provide a more complex chronological pattern (Fig. 2-d; Sup. Tab. 1). However the majority of these dates were obtained from shells that were not taxonomically identified, so the possibility that the obtained C14 ages are older than their actual ages cannot be excluded. Finally, the significant regional variations of the reservoir effect in the Lesser Antilles makes the dates obtained on marine material to be subject to large uncertainties [START_REF] Dinapoli | Marine reservoir corrections for the Caribbean demonstrate high intra-and inter-island variability in local reservoir offsets[END_REF]. As an effect of these numerous issues it was impossible to clearly asses the consistency of the stratigraphy of Roseau on the basis of obtained radio-carbon dates. The first analyses indicated that the site contained material from the Contact period and represented a continuous occupation throughout the whole of Late Ceramic (Troumassoid) period. However, the dating remained poorly resolved, the analysis of the ceramic finds was incomplete, and the study of the faunal assemblage had not yet been carried out. This precluded a clear understanding of the site both in term of chronology and in terms of the behavior of the Amerindian populations.

Materials and methods

14C dating and calibration

In order to improve our understanding of the chronology of the deposit and to test its stratigraphic coherence, we took advantage of twenty new 14 C samples obtained during a study on the isotopic profile of rice rat teeth recovered from the site [START_REF] Goedert | Isotopic ecology and regional extirpation chronology of the extinct Lesser Antillean rat Antillomys rayi[END_REF]. The dates were performed on the dentine of the teeth of single individuals of known species in order to eliminate reservoir and old carbonate effects, in accordance with radiometric hygiene requirements [START_REF] Napolitano | Reevaluating human colonization of the Caribbean using chronometric hygiene and Bayesian modeling[END_REF]. Eight of the twenty radiocarbon dates are of known stratigraphic origin (Fig. 2-d). The other dates were relevant in the context of the isotopic study and contribute to the overview of the chronology of the site but are not useful for interpreting the discrete strata (Fig. 2-b). An additional date was also performed on one of the human remains sent out for palaeoproteomic analysis..The 14C dates were calibrated using Calib online [START_REF] Stuiver | [END_REF]. Dates obtained from shells were calibrated using the Marine20 curve, and those obtained from rodent dentine with the Intcal20 curve (Reimer et al. 2020). Dates obtained from human remains were calibrated using a mixed Intcal/Marine curve. For all calibrations using the Marine curve, referred to the mean value of the marine reservoir corrections (δR) established by for the Caribbean, i.e. -146 +/-114 (DiNapoli et al. 2021) (but see Sup. Text 1 for details regarding human remains).

Archaeological material recovery

The faunal and ceramic assemblages were collected both manually and by sieving with a 0.5 m² sediment column with 2mm wide mesh located in the middle of the B0-B1 trench [START_REF] Richard | Le site archéologique de la plage de Roseau à Capesterre Belle Eau révélateur d'une occupation caraïbe insulaire en Guadeloupe[END_REF]) (Fig. 1). The full assemblage is composed of 12,899 ceramic remains (286 kg) (Sup. Tab. 2) of which 5,021 (177 kg) have been studied and are presented in the current study. The faunal remains consist of 8,591 studied vertebrate bone, but only 6,533 remains are of known stratigraphic origin and therefore relevant to the discussion of the evolution of subsistence strategies.

Ceramic analysis

The ceramic series of Roseau was the subject of two as of yet unpublished studies. The first, carried out by Arie Boomert in 2010 and restricted to a qualitative approach, focused on the Cayo remains [START_REF] Honoré | Évaluation archéologique du site de l'Anse du Coq[END_REF], and a second that was more exhaustive in the form of a Master's dissertation carried out by Alice Le [START_REF] Lay | Étude du mobilier céramique du site de l'arrière-plage de Roseau: Vers une caractérisation culturelle de[END_REF]. The ceramic study presented here is a synthesis of the latter study.

Ceramic remains greater than 3 cm in length from the three main test pits (A0A1, B0B2 and C0C1) (Fig. 1-b) were analyzed. After initial rapid sorting, a short technological study was performed followed by a morphostylistic analysis. The assemblages from the different strata that were identified during the excavation were compared to create a cultural characterization of the occupation sequence. The morphological analysis of the ceramic remains follows a combination of the main typological nomenclatures commonly used in the Lesser Antilles [START_REF] Hofman | search of the native population of pre-columbian Saba (A.D. 400-1450). Part one : Pottery styles and their interpretations[END_REF][START_REF] Bérard | Les premières occupations agricoles de l'arc antillais, migration et insularité. Le cas de l'occupation saladoïde ancienne de la Martinique[END_REF][START_REF] Bonnissent | La céramique du site postsaladoïde de Baie aux Prunes (Plum Bay) : les implications chronologiques et géographiques (Saint-Martin, Petites Antilles)[END_REF]) (see Sup. Fig. 1). The results were compared with various Troumassoid reference collections that are clearly described in the literature: Trou Massé "B" and Micoud in Ste Lucia [START_REF] Mckusick | Pliocene to Pleistocene carbonate systems of the Guadeloupe archipelago, French Lesser Antilles: a land and sea study (the KaShallow project)[END_REF]; L'espérance, Paquemar and Macabou in Martinique [START_REF] Allaire | Later prehistory in Martinique and the Island Caribs: problems in ethnic identification[END_REF]; Spring Bay and Kelbey's Ridge in Saba [START_REF] Hofman | search of the native population of pre-columbian Saba (A.D. 400-1450). Part one : Pottery styles and their interpretations[END_REF]; Mill Reef and Marmora Bay in Antigua [START_REF] Rouse | Excavations at the Indian Creek Site, Antigua[END_REF]; and Baie au Prunes in St. Martin [START_REF] Bonnissent | La céramique du site postsaladoïde de Baie aux Prunes (Plum Bay) : les implications chronologiques et géographiques (Saint-Martin, Petites Antilles)[END_REF]. Cayo elements were characterized after the pioneering work of Boomert [START_REF] Boomert | The Cayo complex of St. Vincent: ethnohistorical and archaeological aspects of the Island Carib problem[END_REF] supplemented by more recent contributions [START_REF] Boomert | Searching for Cayo in Dominica[END_REF][START_REF] Hofman | Colonial Encounters in the Southern Lesser Antilles: Indigenous Resistance, Material Transformations, and Diversity in an Ever-Globalizing World[END_REF][START_REF] Hofman | Island networks: Transformations of inter-community social relationships in the Lesser Antilles at the advent of European colonialism[END_REF].

Zooarchaeological analysis

The study of the different animal taxonomic groups was conducted independently by different specialists sharing a common methodology.

Fish and mammal remains were identified using the comparative collection of the PACEA laboratory (Bordeaux, France). Reptiles were identified using the osteological comparative anatomy collection of the Muséum national d'Histoire naturelle (Paris, France), and published osteological criteria for Iguana (Bochaton et al. 2016c), Diploglossus (Bochaton et al. 2016b), and Pholidoscelis (Bochaton et al. 2019a). The bird bones were identified using the osteological collections housed at the Musée archéologique Edgar Clerc (Le Moule, France); the Paleobiology and Birds Collections of the National Museum of Natural History, Smithsonian Institution (Washington, USA); and the Florida Museum of Natural History, University of Florida (Gainesville, USA).

The quantification units for faunal remains are the Number of Identified Skeletal Parts (NISP) and the Minimum Number of Individual or MNI [START_REF] Lyman | Vertebrate taphonomy[END_REF]). The MNI used here is a frequency MNI as defined by [START_REF] Poplin | A propos du nombre de restes et du nombre d'individus dans les échantillons d'ossements[END_REF]. This was, when possible, preferentially calculated using skull bones for fish but is otherwise calculated on the most abundant anatomical element in a given assemblage. We also use the Percentage of Representation (PR) first used by [START_REF] Brain | The contribution of Namib Desert Hottentots to an understanding of australopithecine bone accumulations[END_REF] and formalized by [START_REF] Dodson | Taphonomic Investigations of Owl Pellets[END_REF] to provide an account of the completeness of archaeological individuals. The analysis of fish trophic levels is based on the work of [START_REF] Wing | Prehistoric fisheries in the Caribbean[END_REF] and [START_REF] Blick | Pre-Columbian impact on terrestrial, intertidal, and marine resources, San Salvador, Bahamas (A.D. 950-1500)[END_REF]. The trophic level of each taxon was defined based on the data from Fishbase (Froese and Pauly 2018) from 1 (primary consumer) to 5 (carnivore) [START_REF] Reitz | Zooarchaeology 2nd Edition[END_REF]. The classification of Caribbean marine ecosystems follows [START_REF] Newsom | On Land and Sea: Native American Uses of Biological Resources in the West Indies[END_REF]. Size reconstruction of Parrotfish (Sparisoma sp.) was based on the measurements and equations defined by Grouard [START_REF] Grouard | Size estimation of pre-Columbian Caribbean fish[END_REF] for the lateral (measurement 3) and central (measurement 1) pharyngeal bones. Size reconstruction of iguanas was based on measurements taken from a broad range of skeletal elements following the work of [START_REF] Bochaton | Describing archaeological Iguana Laurenti, 1768 (Squamata: Iguanidae) populations: size and skeletal maturity[END_REF].

All statistical analyses and tests were performed with the software R (R Core Team 2017) and the base package stats v3.4.3.

Paleoproteomic analysis

Several fragments of large mammals were identified, mostly from level 1. Zooarchaeology by Mass Spectrometry (ZooMS) analysis of five of these bones was carried out in order to obtain taxonomic information to test for the presence of introduced European animal species in the assemblage (see detailed methodology in Sup. Text. 2).

Results

Ceramic analysis

All the recovered remains were included in our technological and morpho-stylistic analyses, the majority of which were collected in the levels 1 and 2 of B0B2 (Sup. Tab. 4 and 5). All fragment types were inventoried by stratigraphic features (Sup. Tab. 6) and the profiles of 567 vessels were reconstructed (Sup. Tab. 7). The morphological data was then cross-referenced with data on decoration (Sup. Tab. 8). It was not possible to clearly characterize each of the layers from a cultural point of view but the overall stratigraphic distribution of the various ceramic components remains chronologically coherent. The occupation of the site of Roseau seems to be primarily associated with the Troumassoid series but also presents a more discrete Cayo component that are described below. A technological analysis was also performed (see Sup. Text 3).

The Troumassoid component:

The greater part of the ceramic series of Roseau is associated with the Troumassoid series. This series covers the Late and Final Ceramic periods [START_REF] Bérard | About Boxes and Labels: A Periodization of the Amerindian Occupation of the West Indies[END_REF]) and presents in the Windward Islands as two sub-series: The Troumassan Troumassoid in the Late Ceramic period and the Suazan Troumassoid in the Final Ceramic period. Features of both sub-series are clearly represented in the Roseau collection, including elements that are present across both entities (tripod griddles, painted Calivigny style motifs, lugs, clay spindle whorls (Fig. 3-a), etc.). A number of features (shapes and decorations) from level 3 and to some extent from level 2 clearly indicate the presence of a Troumassan Troumassoid component in Roseau. This is particularly true of a set of thin walled carinated vessels, cazuelas, various jars, and the fragment of a boat shaped vase (Fig. 3-a-a). Other elements (red slip decorations and large oval ribs) from the same levels are indicative of a more northern influence (Marmoran Troumassoid). This is not surprising as the Guadeloupe islands are considered to be the geographical boundary between the Troumassan and Marmoran Troumassoid sub-series [START_REF] Rouse | Excavations at the Indian Creek Site, Antigua[END_REF]. The higher part of the stratigraphy (level 2 and level 1) is clearly linked to the Suazan sub-series. These layers include a significant presence of simple forms with thick walls and scratched surfaces, finger indented rims or anthropomorphic adornos (Fig. 3-b). Northern influences (Chicoid) could also be distinguished in these upper levels.

The Cayo component: In addition to the Troumassoid component that constitutes the main part of the assemblage, different elements primarily from levels 0 and 1 are indicative of a Cayo Component. The Cayo complex is now known to be distinctly associated with the first colonial Contact period in the Lesser Antilles (1500-1620) and is related to a continental influence (Koriabo) that is visible in the style of ceramic production. This ceramic style has been identified in deposits demonstrating the importance of the contacts and influences involving Island Carib/Kalinago people of the Lesser Antilles, other Amerindian populations, and Europeans during this pre-colonial phase. In these assemblages a Suazan Troumassoid cultural background is associated with elements of European, continental (Koriabo) and northern (Chicoid and Meillacoid) origin [START_REF] Hofman | Colonial Encounters in the Southern Lesser Antilles: Indigenous Resistance, Material Transformations, and Diversity in an Ever-Globalizing World[END_REF][START_REF] Hofman | Island networks: Transformations of inter-community social relationships in the Lesser Antilles at the advent of European colonialism[END_REF]. The Cayo ceramic of Roseau is characterized by the use of sandy and sometimes vegetable tempering agents and a care brought to the surface treatments. In that respect, it clearly differs from the Suazan Troumassoid production which presents a coarser aspect. In terms of vessel shapes, the Roseau collection includes containers that can be compared to the type-shapes 2, 3, 5 and probably also to shape 7 of Boomert topology [START_REF] Boomert | The Cayo complex of St. Vincent: ethnohistorical and archaeological aspects of the Island Carib problem[END_REF]). We found in the series a whole set of Cayo characteristic decorations [START_REF] Boomert | The Cayo complex of St. Vincent: ethnohistorical and archaeological aspects of the Island Carib problem[END_REF][START_REF] Hofman | Colonial Encounters in the Southern Lesser Antilles: Indigenous Resistance, Material Transformations, and Diversity in an Ever-Globalizing World[END_REF][START_REF] Hofman | Island networks: Transformations of inter-community social relationships in the Lesser Antilles at the advent of European colonialism[END_REF]: vertical appliqué nubbin, adornos on vertical strap handles, head lugs on vessel body and punctuated designs.

Revaluation of the stratigraphy and dating of the site

The drawing of the stratigraphic section made by G. [START_REF] Richard | Le site archéologique de la plage de Roseau à Capesterre Belle Eau révélateur d'une occupation caraïbe insulaire en Guadeloupe[END_REF] (Fig. 2-a) shows signs of possible disturbance, such as the presence of gravel at the base of the ravine that suggests the passage of a watercourse, the imbrication of numerous concave-base lenses indicative of erosion, and a marked segregation of archaeological material types similar to the redistribution of material by water flow [START_REF] Reading | The IntCal20 Northern Hemisphere Radiocarbon Age Calibration Curve (0-55 cal kBP)[END_REF]. Such features could be indicators of several stratigraphic perturbations that might have impacted the chronological distinction between the strata of the assemblage [START_REF] Lenoble | Ruissellement et formation des sites préhistoriques : référentiel actualiste et exemples d'application au fossile[END_REF]. The corrections for reservoir effect of the 14C dates previously obtained on marine material shows how uncertain they are and highlight they poor interest to characterize the chronology of the accumulation (Fig. 2-d). In contract, radiocarbon dates obtained on rodent teeth are generally coherent with the stratigraphy, but a few anomalies suggest there may have been some mixing of material between the strata (Fig. 2-b; Sup. Tab. 1). Obtained dates are in accordance with two main periods of occupation periods between the eleventh and fourteenth centuries AD, but a single date also attests to the possible occurrence of rare elements dated to the Contact period in the stratigraphy. The interpretation of the recognized archaeological layers is as follows: 1300 to about AD 1400 for level 1; 1200 -1300 AD for level 2; and 1000 to AD 1150 for level 3. Previous studies of the site identified level 1 in Roseau as Contact period, level 2 as Suazan Troumassoid, and level 3 as Troumassan Troumassoid [START_REF] Richard | Le site archéologique de la plage de Roseau à Capesterre Belle Eau révélateur d'une occupation caraïbe insulaire en Guadeloupe[END_REF]. The presented ceramic analysis, combined with the newly obtained 14C dates, clearly identify most of the site occupation as associated with the Late and Final Ceramic periods. Levels 2 and 3 are dated to the Late Ceramic period with Troumassan and Marmoran cultural components. A second Suazan Troumassoid component that is marginally present in level 2, and accounts for the majority of the ceramic material in level 1, is identified as the Final Ceramic period. Finally, the site was also occupied at the beginning of the Contact period, as is clearly shown by a few minor features in level 1, and more distinctly from pieces characteristic of the Cayo complex recovered from the surface levels (levels 1 and 0). The presence of the Cayo component in level 1 is difficult to quantify, however most of the C14 dates conducted in this level (six out of seven) point to a pre-contact period corresponding to the Late Ceramic period (Suazan Troumassoid cultural current) and only a single date points to the Contact period. As the recovered archaeological elements from level 1 correspond mostly to a Suazan Troumassoid occupation, the majority of the layer cannot be attributed to the Contact period. Traces of contamination are present across the layers, with Cayo ceramic elements occurring in level 2, and a green iguana (Iguana iguana) bone in level 1, a species introduced during the modern era to Guadeloupe. It is possible that a Contact period occupation occurred on the site, creating a substantially altered surface layer that is impossible to delineate. In any case, the site of Roseau documents more than half a millennium of indigenous occupation of the island of Basse-Terre with important continental and northern cultural influences, which can be divided in two periods, the Late Ceramic (level 2 and 3), and the Final Ceramic (level 1).

Zooarchaeological analysis

The zooarchaeological assemblage from Roseau beach is composed of 8,591 bone remains. The complete quantification of the full assemblage is presented in Sup. Tab. 9. Among these remains, 6,533 (76%) were of known stratigraphic origin. The remaining bones are of uncertain origin either because they were collected on the surface or because the record of their stratigraphic origin has been lost since the excavation. The surface of the bones in every layer were often highly damaged with desquamations and presence of roots imprints which made the observation of possible cut marks more difficult. The fragmentation of the remains was not recorded with precision but appeared homogenous in all layers and allowed for an overall good percentage (60%) of the bone to be taxonomically identified.

Fish remains

Fish are the most numerous taxonomic group in the assemblage, represented by 3,859 bone remains of which 1,128 have been identified at least to family, and correspond to an NMI of 222 individuals. A total of 47 taxa (to genus or species) distributed across 32 families have been identified. The families with the most abundant representation are Scaridae (22.1% of the MNI) and Scombridae (12.6% of the MNI) (Sup. Tab. 9). Nine other families represent between 7.2 and 3.6% of the MNI, in order of decreasing abundance: Labridae, Serranidae, Lutjanidae, Carangidae, Belonidae, Haemulidae, Acanthuridae, Centropomidae, and Sphyraenidae (Sup. Tab. 9). The remaining 21 families each represent less than 2% of the total MNI (Sup. Tab. 9). The distribution of anatomical elements indicates that whole fish were transported to the site: all anatomical elements are represented with a good representation of vertebrae (44.75% of the NISP), of the skull and jaw bones (19.8% of the NISP), and of the spines (17.85% of the NISP).

There is a chronological evolution in the composition of the assemblage NISP; the proportion of coral reef, shallow inshore water and pelagic fish species varies between level 1 and levels 2-3 (khi² test; p.val <0.01) with a weaker representation of coral reef fish in level 1 (Fig. 5-a). Levels 2 and 3 do not significantly differ in NISP composition (khi² test; p.val >0.01). This chronological trend is not apparent when comparing the MNI of the different levels. This could be due to either the high diversity of rare species represented in the different levels of the assemblage, or the NMI quantification method overestimating the importance of coral reef fish [START_REF] Lyman | Vertebrate taphonomy[END_REF]. The portion of the assemblage that was manually collected (635 remains) probably also contributed to an overrepresentation of the larger taxa, resulting in a skewed archaeo-ichthyological assemblage profile [START_REF] Casteel | Comparison of column and whole unit samples for recovering fish remains[END_REF][START_REF] Clason | Collecting, sieving and archaeozoological research[END_REF]. In this case, this probably led to an overrepresentation, especially in level 1, of the common snook (Centropomus undecimalis), a fish that can reach more than 1.4 m in length (Froese and Pauly 2018). The remains collected using sieving do seem to confirm however that level 1 is characterized by a better representation of pelagic fishes, especially Scombridae (tuna) (Fig. 5-b).

The mean trophic level represented by the fish remains is stable across the three layers of the site (between 3.8 and 3.7). Sparisoma sp. was the only genus for which size reconstruction of a significant number of specimens was possible. The 38 individual size reconstructions (2 for layer 1 and 36 for layers 2 and 3) indicate that most of the specimens present intermediate sizes between 200 and 360 mm in length (Fig. 5-c). The distribution of these sizes does not follow a normal distribution (Shapiro-Wilk test; p.val<0.01) and no size differences can be observed between the three recognized stratigraphic levels.

Reptile remains

A total of 623 reptile bones have been identified in the complete Roseau assemblage, 391 of known stratigraphic origin information, representing at least 41 individuals (Sup. Tab. 9). Squamates (snakes and lizards) are the most abundant with 473 remains representing at least 43 individuals; in level 1 in particular, squamate bones represent 26% of the total remains. The assemblage is dominated by iguana bones, accompanied by a few remains of two species of Alsophis snake, one of which (Alsophis sp. 2) is now extinct in Guadeloupe (Bochaton et al. 2019b). The other rare squamates are two lizard taxa that are also now extinct in Guadeloupe: an anguid lizard of the genus Diploglossus that has also been identified at other sites on the island (Bochaton et al. 2016b), and a unidentified species of ground lizard (Pholidoscelis sp.) that is frequently represented in Guadeloupian Amerindian assemblages (Bochaton et al. 2019a). The majority of the squamate remains represent at least 33 individual iguana, represented by 444 elements. Previously published osteological criteria (Bochaton et al., 2016b) enable 58 of the skeletal elements to be identified as lesser Antillean iguana (Iguana delicatissima). The only exception is a remain found in level 1, identified as green iguana (Iguana iguana), a species introduced to Guadeloupe during the modern period [START_REF] Breuil | Histoire naturelle des amphibiens et reptiles terrestres de l'archipel guadeloupéen: Guadeloupe, Saint-Martin, Saint-Barthélémy[END_REF]Bochaton et al. 2016a).

Only four cut marks and no burning traces were observed on the iguana material, 7.4% of the bones were unbroken, and the PR was low (14%). These observations do not differs markedly from those of other deposits, as iguana bones rarely present surface alterations of anthropic origins (Bochaton et al. 2016a). It was possible to obtain a size estimation of complete individuals from 78 of the bone remains using published equations [START_REF] Bochaton | Describing archaeological Iguana Laurenti, 1768 (Squamata: Iguanidae) populations: size and skeletal maturity[END_REF].

The distribution of the calculated sizes follows a normal distribution (Shapiro-Wilk test; p. val>0.01) and indicates that all the individuals from the site are of an adult size, with most specimens falling between 350 and 450 mm for snout-vent length (Fig. 5-d). The size of these iguanas is similar to the size observed in the other pre-Columbian sites of Basse-Terre (Bochaton et al. 2016a) and combined with the taphonomic features it may be inferred that these animal were selected, hunted and transported intentionally to the site in order to be consumed. A worked iguana long bone diaphysis with striations was also uncovered, which may have been used as a bead (Fig. 6-d). The stratigraphic origin of this object is however lost. To our knowledge this worked bone is unlike any other objects previously uncovered in Lesser Antillean archaeological deposits, and it is also only the third occurrence of a squamate bone worked [START_REF] Bochaton | First records of modified snake bones in the Pre-Columbian archaeological record of the Lesser Antilles: Cultural and paleoecological implications[END_REF] and the first for a lizard. There were 150 turtle remains uncovered corresponding to at least 5 individuals (Sup. Tab. 9), identified as marine turtles in the family Cheloniidae. The high fragmentation and poor preservation stage of the material preclude any more precise specific or generic identification on the basis of morphology. The majority (113 elements) of the remains are fragments of carapace. Only four elements display cut-marks and one has been burnt, but in general the poor preservation of the bones surfaces prevent any other surface observations.

Bird remains

The full bone assemblage contains 94 bird bones, 53 of which have been identified at least to the level of order (Sup. Tab. 9). The taxonomic diversity is very high, the relatively small sample of identified bones representing at least 15 species and 20 individuals. Because of the scarcity of bird remains and the lack of stratigraphic information for the most part, it is not possible to assess the differences in bird diversity between the layers. Procellariiforms are the taxa with the greatest representation (34% of identified bird NISP) followed by Passeriformes (23%) and Columbiformes (19%). The remaining 24% represent five different orders: Anseriformes, Pelecaniformes, Gruiformes, Strigiformes and Psittaciformes. The Black-capped Petrel (Pterodroma hasitata) is among one of the more remarkable taxa uncovered. This species went extinct during historical times in Guadeloupe and remains have only previously been recovered at the Amerindian site of Rivière du Baillif (Grouard 2001a). Other notable species include the Forest Thrush (Turdus lherminieri) in layer 3, indicating the proximity of a tropical moist forest [START_REF] Parashuram | The Forest Thrush Turdus lherminieri prefers mature mesic forest with dense canopy[END_REF]; a giant owl similar to the fossil species of the Greater Antilles and to the Pleistocene remains of Tyto sp. found in Barbuda [START_REF] Steadman | A new species of exctinct barn owl (Aves: Tyto) from Barbuda, Lesser Antilles[END_REF][START_REF] Suárez | Systematics and distribution of the giant fossil barn owls of the West Indies (Aves: Strigiformes: Tytonidae)[END_REF] suggesting the occurrence of large owls in pre-contact Amerindian Guadeloupe; and an Amazon parrot (Amazona sp.) not previously mentioned in the other archaeological sites of Basse-Terre. The past occurrence of Amazona in the Guadeloupe Islands is, however, mentioned in historical sources [START_REF] Williams | The Historic and Prehistoric Distribution of Parrots (Psittacidae) in the West Indies[END_REF], and a few bone remains have been recovered from two Ceramic Age sites in Marie-Galante and in the La Désirade islands (Grouard 2001a;[START_REF] Olson | New evidence of Ara autochthones from an archeological site in Puerto Rico: a valid species of West Indian macaw of unknown geographical origin (Aves: Psittacidae)[END_REF].

Mammal remains

The majority of the mammal remains in the site assemblage are small rodents. Among the 582 remains identified as rodents, 405 are of known stratigraphic origin and represent a minimum of 35 individuals. This material was recovered primarily from levels 2 and 3 (93%) and is mostly comprised of the Barbuda and Guadeloupe oryzomyine rat (Antillomys rayi) (Fig. 6-b) and of agouti (Dasyprocta leporina) (Fig. 6-c). The former is the most abundant mammal in level 2 (n=130, 71% total level NISP), the latter most abundant in the level 1 (n=131, 67%).

The absence of juvenile bones, and the presence of traces of digestion combined with cut marks and traces of burning on a small portion of the remains (n=32) of both species leaves little doubt of the anthropogenic nature of this bone accumulation. In addition to the remains of small mammals, eighteen remains of large mammals were identified exclusively from level 1. One of these is the distal part of a manatee rib (Fig. 6-a). This constitutes the first Pre-Columbian archaeological occurrence of a non-worked bone of this animal in Guadeloupe (Ramos [START_REF] Roca | Zooarcheological Evidence on the Utilization of Aquatic Mammals in Northern South America and the Caribbean: A Contribution to Long-Term Biological Conservation[END_REF]. The other large mammal remains are heavily fragmented and impossible to identify from morphological criteria. Five of the fragmented bones were selected for palaeoproteomic analysis (see below) and all the fragments were identified as human. It is therefore extrapolated that all the fragmented bone is of human origin; no markings of any sort were observed on this material and there is no available evidence regarding its origin and depositional history.

Paleoproteomics analysis

All five samples analysed were identified as hominid. The B marker in all samples is present at m/z 1477, which is highly diagnostic for humans, Neanderthals, and Denisovians, separating them from other primates (Brown et al. 2016). Given the archaeological context, the identification as human may be readily accepted and the hypothesis of the presence of domestic mammals in the stratigraphy of Roseau rejected.

General zooarchaeological remarks

The proportions of the vertebrate taxa (fish, mammals, reptiles, birds) differ significantly between each of the three levels at Roseau (pair wise chi² test; p.val <0.01). Across the layers there is a progressive increase in the proportion of terrestrial fauna, from 6% in level 3 to 12% in level 2, and 49% in level 1. In addition to this transition there are two secondary chronological changes. The first is a shift from the exploitation of a native small mammal (Antillomys rayi) that represent 70% of the mammal remains in level 2 and 3, towards that of an introduced rodent (Dasyprocta leporina), representing 75% of the small mammal remains in level 1. There is also a shift from coral reef fishing toward more pelagic fishing. Our zooarchaeological analysis provides no evidence that this evolution is a reflection of taphonomic bias as the quality of the preservation and the fragmentation of the remains are homogeneous across the deposit and all types of taxa uncovered exhibit evidence of human exploitation. There is also no zooarchaeological evidence of an overexploitation of the marine environments that may have forced the Amerindian groups towards more terrestrial subsistence strategies. This is demonstrated by the absence of evolution of the mean trophic level and of the sizes of the fished fishes in the different layers. The shell assemblage may provide complementary information to the pattern observed in the vertebrate assemblage, but this study has not yet been conducted.

DiscussionThe Roseau zooarchaeological assemblage in the regional context

The bone assemblage in the lower levels of the site (2 and 3) is mostly composed of marine vertebrates, typical of most Lesser Antillean Amerindian assemblages. However the upper level (1), with its notable representation of reptiles and terrestrial vertebrates, bears a greater resemblance to the small number of Lesser Antillean Amerindian vertebrate assemblages that deviate from the general tendency towards a marine profile, and instead exhibit a composition containing less than 60% of marine vertebrates. Examples of other sites with a more vertebrate terrestrial profile include Hichmans on Nevis [START_REF] Newsom | On Land and Sea: Native American Uses of Biological Resources in the West Indies[END_REF], Hope Estate on Saint-Martin [START_REF] Newsom | On Land and Sea: Native American Uses of Biological Resources in the West Indies[END_REF]), Trants on Montserrat [START_REF] Reitz | Archaeology of Trants, Montserrat. Part 2. Vertebrate Fauna[END_REF], and Morel in Guadeloupe (Grouard 2001b[START_REF] Grouard | Modes de vie des Précolombiens des Antilles françaises[END_REF].

The plentiful diversity of fish species in the zooarchaeological vertebrate assemblage of Roseau is similar to most Guadeloupian and Lesser Antillean assemblages (Grouard 2001a;[START_REF] Newsom | On Land and Sea: Native American Uses of Biological Resources in the West Indies[END_REF][START_REF] De Waal | Pre-Columbian social organization and interaction interpreted through the study of settlement patterns: An archaeological case-study of the pointe des Châteaux, La Désirade and les Îles de la Petite-Terre micro-region[END_REF]. The only unusual fish taxa uncovered are Bothidae and Scorpaenidae, which have not been found previously in the archaeological record of Guadeloupe. The abundant presence of Scaridae is common in zooarchaeological assemblages as coral reefs were intensively exploited by Lesser Antillean Amerindians (Grouard 2001a;Wing 2001a, b;[START_REF] Newsom | On Land and Sea: Native American Uses of Biological Resources in the West Indies[END_REF][START_REF] De Waal | Pre-Columbian social organization and interaction interpreted through the study of settlement patterns: An archaeological case-study of the pointe des Châteaux, La Désirade and les Îles de la Petite-Terre micro-region[END_REF].

Bird remains found at Roseau have a similar profile to the other lesser Antillean Amerindian sites with a similar proportion of the principally represented orders (in decreasing order of importance): Procellariiformes, Passeriformes, Columbiformes, and water birds (Anatidae, Ardeidae, and Ralidae). However, with 15 taxa present in the assemblage, the Roseau bird series displays a remarkably high taxonomic diversity despite the limited size of the assemblage. In comparison, the number of avian taxa in Guadeloupian pre-Columbian assemblages ranges between 1 and 7 [START_REF] Wing | Prehistoric fishing economies of the Caribbean[END_REF]Grouard 2001a;[START_REF] Olson | New evidence of Ara autochthones from an archeological site in Puerto Rico: a valid species of West Indian macaw of unknown geographical origin (Aves: Psittacidae)[END_REF][START_REF] Stouvenot | L'abri sous roche Cadet 3 (Marie-Galante): un gisement à accumulations de faune et à vestiges archéologiques[END_REF]. This could reflect both the variety of environments surrounding the site (mesophilic forest, xerophilic forests, and coastal habitats), and possibly the collaboration of a paleo-ornithologist in the study.

In respect to reptiles, Roseau does not present any notable differences in comparison to other assemblages from Guadeloupe in terms of the taxonomic diversity.

Evolution of fishing techniques

The size of Parrot fish (Sparisoma sp.) from the site indicates that medium sized specimens (between 160 and 279 mm in total length) of sub-adult proportions are the most represented. This could indicate the use of selective fishing techniques (fishnet, trap, hooks) in reef areas (Grouard 2001a). Fishing techniques vary markedly depending on the depth and morphology of the seabed [START_REF] Bonniol | Terre-de-Haut des Saintes. Contraintes insulaires et particularisme ethnique dans la Caraïbe[END_REF]) so it is difficult to propose which specific methodologies may have been practiced by the people who occupied the site.

The possible increase of deep sea water fishing (Scombridae) may reflect a technological evolution with an increasing use of boats in fishing activities. Ethnographic comparisons may provide examples of the methods that could have been used. In the eighteenth century the most commonly used technique to fish pelagic fish was trawling with three fishermen in the boat, two maintaining the boat against the winds and currents and the third managing the lines attached to wood or bone hooks [START_REF] Guillou | Optimal diet breadth theory as a model to explain variability in Amazonian hunting[END_REF]. This technique enables a catch of a maximum of 500 kg of fish for a single boat and is still the method the most commonly used in the present day [START_REF] Reynal | Le redéploiement de la pêche antillaise vers les grands poissons pélagiques[END_REF]. In general, notwithstanding whichever techniques may have been used, deep sea fishing methods require more human and material investment that the fish methods applied in areas of coral reef (Grouard 2001a;[START_REF] Newsom | On Land and Sea: Native American Uses of Biological Resources in the West Indies[END_REF].

Evolution of vertebrate exploitation strategies

The faunal vertebrate assemblages differ notably between level 1 dating to the Contact/Final Ceramic period and levels 2 and 3 dating to the Late Ceramic period. The vertebrate consumption shifts from a nearly exclusive exploitation of coral reef marine resources to a mixed exploitation of terrestrial resources and a greater frequency of pelagic fishing. This shift contradicts the general regional trends of the increasing role of coral reef fish in the subsistence economy during the Ceramic Age [START_REF] Grouard | Size estimation of pre-Columbian Caribbean fish[END_REF]) and instead aligns with the development of more specialized economies having a higher focus on pelagic fishing in volcanic islands [START_REF] Grouard | Subsistance et mode de vie des premiers habitants de Guadeloupe (500 av. -1500 ap[END_REF]. Roseau beach is situated near to a river mouth and at the interface between the reef formation of the Grand Cul de Sac marin and the deep sea of the Saintes channel. Both coral reef and pelagic fishing would therefore have been possible, as tuna have been documented following the streams in the Saintes channels between January and June [START_REF] Bonniol | Terre-de-Haut des Saintes. Contraintes insulaires et particularisme ethnique dans la Caraïbe[END_REF]. In addition, two other Guadeloupian sites that exhibit a notable proportion of pelagic fish in their zooarchaeological assemblages (Grande Anse and Riviére de Baillif) are also situated in the southern area of the Basse-Terre Island (Grouard 2001a).

Data from terrestrial fauna indicates that Lesser Antillean Rice rats were initially hunted and then replaced by the hunting of agouti. Agoutis were already present in Guadeloupe at the beginning of the Saladoid period (Grouard 2001a) and were probably available for predation in Guadeloupe during the first occupation phase of Roseau. The increase of their proportion in the assemblage could be due to a release of hunting pressure. Indeed, cases where the environment is not over-exploited; foragers tend to restrict their hunting spectrum around the most energy-efficient species [START_REF] Macarthur | On Optimal Use of a Patchy Environment[END_REF] and in neotropical environments, agoutis (and iguanas) are high-ranking resources [START_REF] Guillou | Optimal diet breadth theory as a model to explain variability in Amazonian hunting[END_REF][START_REF] Keegan | Transition from a terrestrial to a maritime economy: A new view of the crab/shell dichotomy[END_REF][START_REF] Alvard | Testing the "ecologically noble savage" hypothesis: Interspecific prey choice by Piro hunters of Amazonian Peru[END_REF]) certainly offering a higher energy return than that provided by the Rice rats. The management of Agoutis by human populations is an alternative hypothesis and an isotopic study similar to the work recently conducted on archaeological Bahamas hutia [START_REF] Lefebvre | The zooarchaeology and isotopic ecology of the Bahamian hutia (Geocapromys ingrahami): Evidence for pre-Columbian anthropogenic management[END_REF]) would be needed to investigate this question. In parallel with this shift in rodent exploitation, iguanas also began to be hunted, a phenomenon corroborated by 17 th and 18 th centuries historical sources (Du Tertre 1654; Monpilliers 1654; Grunberg 2013), and these lizards are even more numerous than rodents in level 1. This observation could be related to the similar pattern observed on agoutis but is otherwise is difficult to comment further as there are no clear patterns of squamate exploitation in Amerindian deposits, and such behavior may primarily reflect socio-cultural tendencies that are impossible to document.

A Cayo component in the ceramic assemblage marking the arrival of exogenous cultural influences in the Lesser Antilles is present in the layer 1 in which the changes in vertebrate exploitation were observed. However, this component is probably too minor to fully explain the changes. Thus, the most likely hypothesis to explain the observed vertebrate exploitation shift is unlikely related to any strong cultural evolution/change/replacement and probably to more subtle causes, some of which are discussed below.

There are very few examples in the Lesser Antilles of an intra-site chronological vertebrate exploitation transition. A similar but less spectacular transition was observed at the site of Keldey's Ridge in Saba (Wing 2001a). In the Troumassoid site of Sabazan (Grenadines) (Giovas 2016b) the inverse was suggested with a putative progressive decrease in terrestrial vertebrates over time but the bone material was not abundant enough to draw clear conclusions. These two examples alone show that either that there is no simple regional trend as has been previously hypothesized [START_REF] Jones | Dietary Change and Human Population at Indian Creek, Antigua[END_REF][START_REF] Wing | Human exploitation of animal resources[END_REF] or that global patterns are still impossible to determine due to the lack of data describing the most recent Amerindian periods in the Caribbean. In any case, the Roseau vertebrate assemblage confirms that terrestrially oriented diets are not specific to the earliest periods and can occur in the Final Ceramic, further confirmed by isotopic studies [START_REF] Stokes | A biogeographic survey of prehistoric human diet in the West Indies using stable isotopes[END_REF][START_REF] Laffoon | Human dietary assessment in the Pre-colonial Lesser Antilles: New stable isotope evidence from Lavoutte, Saint Lucia[END_REF]. Explaining subsistence behavior modification is complex as it does not seem to strictly adhere to either chronological or regional trends. As is demonstrated in this study, the shift at Roseau cannot be explained by an erosion of the coral reef and it is likely that this type of transition follows site-specific logic and emerges independently from chronology and broader cultural currents. Several hypotheses could nevertheless be formulated to explain the chronological changes observed at Roseau. First, the change could reflect a seasonal occupation as has been clearly demonstrated for Plum piece [START_REF] Hofman | Plum piece: evidence for archaic seasonal occupation on Saba, northern lesser Antilles around 3300 BP[END_REF] and hypothesized for several other Amerindian sites (e. g. [START_REF] Antczak | Pre-Hispanic Fishery of the Queen Conch, Strombus gigas, on the Islands off the Coast of Venezuela[END_REF][START_REF] Serrand | Exploitation des invertébrés par les sociétés précolombiennes des Petites Antilles[END_REF]. However, this hypothesis is not supported by the isotopic data collected on Rice rats [START_REF] Goedert | Isotopic ecology and regional extirpation chronology of the extinct Lesser Antillean rat Antillomys rayi[END_REF] although the question of seasonal exploitation of fish remains open. Second, the practice of garden hunting [START_REF] Linares | Garden hunting" in the American tropics[END_REF]) could explain the abundance of agouti in the later phase of Roseau. It would need to be accompanied by other hunting strategies as garden hunting alone could not account for the exploitation of other taxa including Procellariiforms birds. Third, a better supported hypothesis would be that of a release of the hunting pressure on terrestrial fauna possibly compatible with discontinuous occupation of the site which led to a better representation of large size/high ranking animals in the more recent layers [START_REF] Guillou | Optimal diet breadth theory as a model to explain variability in Amazonian hunting[END_REF]Grouard 2001b;Wing 2001b). This could also be in accordance with the better representation of large offshore fishes in the same layer a pattern similar to the one suggested by the isotopic data of the Lavoutte Amerindian site [START_REF] Laffoon | Human dietary assessment in the Pre-colonial Lesser Antilles: New stable isotope evidence from Lavoutte, Saint Lucia[END_REF]. Finally, a cultural explanation should not be disregarded. For example, examples of Lesser Antillean Amerindian cultural food choices have been well documented historically by European chroniclers in the form of food taboo. Several authors testified that seventeenth century Amerindians refused to consume manatee as it was considered too fatty and was supposed to bring back diseases [START_REF] Grunberg | Textes anonymes. Anonyme de Carpentras, Anonyme de Grenade[END_REF]. The native Lesser Antillean Amerindians also refuse to hunt Boa snakes that were reputed to avenge themselves on the grandchildren of the hunters. Other snakes species, as well as eels believed to be their sisters, were also not killed or consumed [START_REF] Grunberg | Textes anonymes. Anonyme de Carpentras, Anonyme de Grenade[END_REF]. These testimonies find an echo in the archaeological record as the bones of the above mentioned taxa lack any trace of consumption, and are either very rarely found or found only as manufactured artifacts in Amerindian deposits (Ramos Roca and Perez Iglesias 2015; Bochaton et al. 2019b;[START_REF] Bochaton | First records of modified snake bones in the Pre-Columbian archaeological record of the Lesser Antilles: Cultural and paleoecological implications[END_REF].

Conclusion

The new study of the Roseau material underlines the complexity and variability of Ceramic Amerindian subsistence behaviors. The site suffers from the same limitations as many other regional excavations in terms of the limited portion of the site available for excavation and the low quality chronological and spatial characterization as a result of both biostratigraphic perturbation and poor preservation. The invertebrate assemblage of the site also remains unstudied and could provide valuable complements to our observations. However, despite these limitations, the zooarchaeological vertebrate material provides evidence for a previously unobserved exploitation strategy shift from predominantly marine resources with an emphasis on coral reef fish to terrestrial resources supplemented by pelagic fish. The rational for this change in subsistence is difficult to interpret considering how little is known of the chronology and cultural traits of the Ceramic Age Amerindians of the Lesser Antilles. Despite its rich archaeological record and the numerous hypotheses that have driven zooarchaeological research in the region, no predominant pattern in subsistence strategy has emerged. Different strategies exist within the same period as a result of a complex intersection of cultural, ecological, and environmental contexts providing a picture of a highly diverse and adaptive set of regional substance strategies that were present in the Lesser Antilles during the Ceramic Age. The quality of zooarchaeological data present from often limited excavations allows for observations of changing subsistence strategies. Increased excavations and improved chronologies at sites across the region will allow for a better understanding of the nature of these subsistence changes and the further investigation of the environmental, ecological, or cultural drivers for these behavior changes.

Fig. 1 :

 1 Fig. 1: a) Map of the Guadeloupe Islands with isobaths (-200m) from Münch et al. (2013) indicating the location of the Roseau site. b) Chart of the site with locations of the trenches (A0-A1, B0-B2, and C0-C1), test pits (TP1, TP2, and TP3) and sieving column.

Fig. 2 :

 2 Fig. 2: a) Stratigraphy of the trench B0-B2 (modified from Richard, 2003); b) Radiocarbon dates obtained from rodent teeth from throughout the Roseau assemblage; c) Rodent teeth and human bone (Beta-521489) dates with known stratigraphic origin; d) Previously published and unpublished dates obtained mainly from shell, but also from another type of undefined carbonate (Ly-12009), and human bone (Ly-2217). The labels along the y-axis indicate the laboratory code of each sample.Dates on rodent teeth were calibrated with the Intcal20 curve, dates on shell and carbonate with the Marine20curve, and dates on human bone with a mixed calibration curve assuming a 33% contribution of marine carbon for the individual from level 1 (Beta-521489) and 50% for the specimen from level 2 (Ly-2217). The line represents a confidence interval that includes 95.4% of the probability distribution.

Fig. 3 :

 3 Fig. 3: a) Troumassan Troumassoid ceramic remains: a. Boat-shaped vessel (surface), b. Round bowl with Calivigny painted design (Layer 2), c., d. & e. Carinated unrestricted vessels (Layer 2), f. Cazuela with broad incisions and red engobe (Layer 3). b) Suazan Troumassoid ceramic remains: g. to j.: Anthropomorphic adornos (Layer 1 and surface), k.: Scratched shards (Layer 2), l. to p.: Suazan Troumassoid type vessels.

Fig. 4 :

 4 Fig. 4: Cayo style vessel shapes and decorations: a.: Cayo type form 3 (Layer 1), b.: Cayo type form 5 (Layer 1), c.: Bowl with a punctuated design on the lip (Layer 2), d. et e.: Necked jars (Layer 1), f.: Bowl with elongated vertical appliqué nubbins with transversal nicks (Layer 1), g.: Cayo type form 5 and associated typical decorations (Layer 2 and Layer 1), h.: Cayo style jar with inflected contours (Layer 1), i.: Cayo style design (Surface).

Fig. 5 :

 5 Fig. 5: a) Proportion of the ecological niches represented by the fish remains in the different layers using the total NISP of all identified bone remains; b) Proportion of the ecological niches represented by the fish remains in the different layers using the NISP of the identified bone remains collected through sieving only; c) Distribution of the size of archaeological specimens of Sparisoma sp. (N=38); d) Distribution of the size of archaeological specimens of Iguana (N=623).

Fig. 6 :

 6 Fig. 6: a) Manatee rib found in the layer 1; b) Right maxilla of Antillomys rayi from layer 2; c) Right mandible of Dasyprocta leporina from layer 1, d) Worked long bone diaphysis of Iguana sp. possibly used as a bead of unknown stratigraphic origin.

This study was funded by the FEDER program 2016-2020 ''Ecosystème insulaire tropical, réponse de la faune vertebrae terrestre à 6 000 ans d'anthropisation de la Guadeloupe'' (ECSIT), operated by the CNRS and funded by a European PO-FEDER 2014-2020 grant (grant n°2016-FED-503), the Guadeloupe Regional Council, and the DAC of Guadeloupe. The palaeoproteomic analysis was funded by the Max Planck Society. Conflicts of interest/public repository in the Service Régional de l'reviewers whose comments helped us to improve the quality of this paper. This study was funded by the FEDER program 2016-2020 ''Ecosystème insulaire tropical, réponse de la faune vertebrae terrestre à 6 000 ans d'anthropisation de la Guadeloupe'' (ECSIT), operated by the CNRS and funded by a European PO-FEDER 2014-2020 grant (grant n°2016-FED-503), the Guadeloupe Regional Council, and the DAC of Guadeloupe. We are also grateful to Jean-Baptiste Mallye, Stéphane Rottier, and Violaine Palacio for their assistance in the identification and digitization of the large mammal bones selected for ZooMS analyses. We also thank Véronique Laroulandie and David Steadman for their advice regarding the identification of select bird remains, as well as C.

data used in this study are available in the text of the paper and in the supplementary materials. the archeological context of the Roseau material. We are also grateful to the two anonymous


Vincent Delmas

Valentin Diez-Cabanes

Colin Van Dyck

Elke Scheer

Karine Costuas

Jérôme Cornil

On the Reliability of Acquiring Molecular Junction Parameters by Lorentzian Fitting of I/V curves

Keywords: Molecular junctions, electronic transport, thermoelectricity, Fermi level alignment, organometallic compound, NEGF-DFT, computational chemistry

Fitting the I/V curves of molecular junctions by simple analytical models is often done to extract relevant molecular parameters such as energy level alignment or interfacial electronic coupling to build up useful property-relationships. However, such models can suffer from severe limitations and hence provide unreliable molecular parameters. This is illustrated here by extracting key molecular parameters by fitting computed voltage-dependent transmission spectra and by comparing them to the values obtained by fitting the calculated I/V curves with a typical Lorentzian model used in the literature. Doing so, we observe a large discrepancy between the two sets of values which warns us about the risks of using simple fitting expressions. Interestingly, we demonstrate that the quality of the fit can be improved by imposing the low bias conductance and Seebeck coefficient of the junction to be recovered in the fitting procedure.

The field of molecular electronics aims at developing functional nano-electronic devices by inserting molecules between two metallic electrodes. The current-voltage (I/V) curves of such devices can be measured by several techniques such as conductive-AFM for self-assembled monolayers (SAMs) or Mechanically Controlled Break Junction (MCBJ) for single molecules. 1- 4 The electrical characteristics are governed by two key molecular parameters which are often voltage dependent: the energetic position of the molecular electronic levels responsible for charge transport with respect to the Fermi energy of the electrodes (e 0 ) which is not easy to measure [START_REF] Fereiro | Direct Optical Determination of Interfacial Transport Barriers in Molecular Tunnel Junctions[END_REF] and the electronic coupling strength between these orbitals and the electronic states of the electrodes (G) that cannot be accessed directly experimentally. Although Ultraviolet/Inverse Photoelectron Spectroscopy (UPS/IPES) are typically used to infer the position of the electronic levels with respect to the Fermi level of a substrate in a SAM configuration, the relative position of the electronic levels is expected to be different in a molecular junction configuration (due to additional interfacial electronic coupling, built-in fields [START_REF] Van Dyck | Large Built-In Fields Control the Electronic Properties of Nanoscale Molecular Devices with Dipolar Structures[END_REF] and image charge effects when a second electrode is introduced). At the present stage, e 0 and G parameters are mostly deduced by fitting experimental I/V curves, considering that the electronic transmission at the origin of the current is of Breit-Wigner resonance type (Lorentzian-type shape); this model considers a single molecular level (generally the HOMO or LUMO of the molecule) at the energy e 0 coupled to the electronic states of the electrodes (Figure 1). [START_REF] Huisman | Interpretation of Transition Voltage Spectroscopy[END_REF][START_REF] Bâldea | Revealing Molecular Orbital Gating by Transition Voltage Spectroscopy[END_REF][START_REF] Cuevas | Molecular Electronics: An Introduction to Theory and Experiment[END_REF][START_REF] Bâldea | Ambipolar Transition Voltage Spectroscopy: Analytical Results and Experimental Agreement[END_REF][START_REF] Briechle | Current-Voltage Characteristics of Single-Molecule Diarylethene Junctions Measured with Adjustable Gold Electrodes in Solution[END_REF][START_REF] Xie | Experimental and Theoretical Analysis of Nanotransport in Oligophenylene Dithiol Junctions as a Function of Molecular Length and Contact Work Function[END_REF][START_REF] Isshiki | Investigation on Single-Molecule Junctions Based on Current-Voltage Characteristics[END_REF][START_REF] Xie | Determination of Energy-Level Alignment in Molecular Tunnel Junctions by Transport and Spectroscopy: Self-Consistency for the Case of Oligophenylene Thiols and Dithiols on Ag, Au, and Pt Electrodes[END_REF] The full width at half maximum of this Lorentzian reflects the amplitude of the electronic coupling G. The Lorentzian-type expression of the electronic transmission t(E) at a given energy E is expressed as:

𝜏 𝐸 =
4 𝛤 𝐿 𝛤 𝑅 𝐸 -𝜖 0 2 + 𝛤 𝐿 + 𝛤 𝑅 [START_REF]AFM Studies on (Bio)Molecular Systems: Unravelling the Nanoworld[END_REF] (1)

In the case of symmetric contacts between the molecule and the two electrodes, G L and G R are equal (G L = G R = G) leading to the simplified expression:

𝜏 𝐸 = 4𝛤 2 𝐸 -𝜖 0 2 + 4𝛤 2 (2)
It is important to stress that this model suffers from severe limitations in considering that only one molecular transporting level is present close to the Fermi level, as evidenced theoretically by Neaton and co-workers. [START_REF] Quek | Thermopower of Amine-Gold-Linked Aromatic Molecular Junctions from First Principles[END_REF] Using the DFT + S (i.e., with self-energy corrections) formalism, some junctions show electronic transmissions which deviate importantly from a Lorentzian-shape curve. [START_REF] Isshiki | Investigation on Single-Molecule Junctions Based on Current-Voltage Characteristics[END_REF] The single-level model is indeed expected to break down for molecules displaying several closelying energy levels in the transmission window. A second important hypothesis of this fitting model is to consider that the molecular parameters G and e 0 are bias voltage independent. In reality, and depending on how the applied voltage drops across the molecule, the level energy may be bias-dependent. Recent calculations clearly demonstrated that G is a bias dependent parameter. [START_REF] Liu | Voltage Dependence of Molecule-Electrode Coupling in Biased Molecular Junctions[END_REF] Moreover, this model does not account for the typical decrease in the intensity of the transmission peak with increasing bias. Finally, if there are several molecules in the junctions, the total transmission is not simply the sum of the transmission spectrum of the individual molecules so that a prefactor accounting for cooperative effects should be introduced. Accordingly, we will only focus on single-molecule junctions in the following. Despite its significant restrictions, this model has been widely exploited by experimentalists to shed light on the electronic structure of molecular junctions and to establish relationships between the I/V characteristics and the electronic structure of the molecular junction. In this context, our paper aims at addressing the reliability of this analytical procedure using quantum chemistry (QC) as a tool able to provide in parallel I/V curves that can be fitted using the same models as previously described in literature and the actual calculated electronic parameters of a single-molecule junction based on calculated transmission functions. This allows us to evaluate the accuracy of the fitting models in recovering a correct amplitude for the two parameters using I/V curves in comparison to the values calculated independently. It is important to emphasize at this stage that the scientific evidences given below are not dependent on the level of theory used. The present work highlights that much care has to be taken while using the single-level fitting procedure to extract the physical characteristics of a molecular junction.

In order to exemplify the problems that can arise from I/V curve fittings using this single-level model, we choose to evaluate the transmission properties of the trans-Ru(TMA)(C≡C-C 6 H 4 -SH) 2 molecule (TMA = 1,5,9,13-tetramethyl-1,5,9,13-tetraazacyclohexadecane) grafted to gold electrodes. This system has been chosen as study case for several reasons. First, it is a symmetric molecular junction in which the metallic center Ru(II) is coordinated in a trans arrangement to conjugated (thiol)aryl-acetylide organic linkers. The rest of the central metal coordination sphere is completed by a tetra-chelating ligand via nitrogen atoms (Figure 2). This pseudo-octahedral environment stabilizes the metal center to fulfill the 18-electron rule conferring a high thermodynamic stability to the system. As lots of organometallic complexes, it displays a weak oxidation potential in comparison to most organic conjugated molecules, [START_REF] Costuas | Polynuclear carbon-rich organometallic complexes: clarification of the role of the bridging ligand in the redox properties[END_REF] a feature which promotes molecular levels close to the Fermi energy of the electrodes. Since this system is known in its molecular form [START_REF] Wong | Spectroscopic Studies and Structures of Trans -Ruthenium(II) and Ruthenium(III) Bis(Cyanide) Complexes Supported by a Tetradentate Macrocyclic Tertiary Amine Ligand[END_REF][START_REF] Doro | The Versatile Ruthenium(II/III) Tetraazamacrocycle Complexes and Their Nitrosyl Derivatives[END_REF] and closely-related molecular junctions have been successfully investigated experimentally by us and others [START_REF] Meng | Photo-Modulable Molecular Transport Junctions Based on Organometallic Molecular Wires[END_REF][START_REF] Milan | Metal Bis(Acetylide) Complex Molecular Wires: Concepts and Design Strategies[END_REF] it is highly suitable to experimental investigations. It has been chosen as study case among a large series of candidates that we have been screening since its calculated transmission properties show a high transmission peak close to the Fermi level with a quasi-Lorentzian shape, as required for this study. The molecular junction is built by grafting the molecule to two gold electrodes via sulfur-gold bonds on the hollow site of the gold (111) surface (thiol hydrogens removed, see Figure S1). The transmission spectra and I/V curves have been simulated in the coherent regime at the DFT+NEGF level using the ATK package software from Synopsys (see Supporting Information (SI) for additional computational details). [START_REF] Quantumatk | 12 Synopsys[END_REF] The calculated transmission spectrum given in Figure 3b at zero bias (DV = 0 V) displays a Lorentzian peak centered at e 0 = -0.214 eV below the Fermi level. A very narrow peak (hence not contributing to the current) is also found at e 1 = -0.4 eV and is associated to other states involving the molecular backbone, (see Figure S2). [START_REF] Porod | Resonance-Antiresonance Line Shape for Transmission in Quantum Waveguides with Resonantly Coupled Cavities[END_REF][START_REF] Göres | Fano Resonances in Electronic Transport through a Single-Electron Transistor[END_REF][START_REF] Lambert | Basic Concepts of Quantum Interference and Electron Transport in Single-Molecule Electronics[END_REF] Nonetheless, the main transmission peak can be accurately fitted by a single level as shown below.

The Landauer formula used to estimate the current is given in Eq. 3, where µ L,R is the chemical potential of the left (L) and right (R) electrode, T the temperature, k b the Boltzmann constant, and f L,R is the Fermi-Dirac function:

𝐼 = 2𝑒 ℎ 𝜏 𝐸,
In the following, we will also refer to the Seebeck coefficient S and the conductance G. S corresponds to the bias that can be generated by a difference of temperature between the two electrodes (S = -DV/DT) 8,27-30 S has been measured for many molecular junctions. [START_REF] Widawsky | Simultaneous Determination of Conductance and Thermopower of Single Molecule Junctions[END_REF][START_REF] Cui | Peltier Cooling in Molecular Junctions[END_REF] This parameter can be calculated using the transmission spectrum at zero bias (in the linear regime approximation) and is formally defined at zero current I. A simplification of the current equation (Eq. 3) can thus be done (see SI, Eqs. S1-4) leading to Eq. 4. In this expression, the L n terms are incorporating integrals of the Fermi-Dirac function at equilibrium (f eq ) (Eq. 5, Eq. 6) which describes the distribution of electrons/holes over energy states in the electrodes.

𝐿 K = - 2𝑒 ℎ 𝜏 𝐸, 𝑉 𝐸 -𝜇 LM K 𝜕𝑓 LM 𝜕𝐸 𝑑𝐸 (4)
𝑓 LM = 1 exp 𝐸 -𝜇 LM 𝑘 F 𝑇 + 1 (5)
The conductance G is calculated within the linear regime approximation as: 𝐺 = 𝐿 J 𝐺 J , (7) with G o the quantum of conductance (77.48 µS). The coupling (Γ) and the energy (e 0 ) can be deduced in the single-level approximation directly from each calculated transmission spectrum by fitting the peak closest to the Fermi level by a Breit-Wigner function (Eq. 2). The implementation of the fitting procedures is detailed in SI. The obtained values can be considered as benchmark reference values for this study since they are directly issued from the DFT+NEGF transmission (t) calculations (labelled later as Γ t and e 0-t ). One couple of values Γ t and e 0-t is thus obtained at each voltage (Table S1). The Γ t and e 0-t values given in Table 1 for several ranges of bias are the averaged values over the considered voltage range. e 0-I/V (Eq. 3). This was done using several voltage ranges in the I/V curve: (i) from 0 to 100 meV, a range of bias in which the current is proportional to the bias (linear regime); the transmission properties are slightly changed within this small potential window (no noticeable energy shift of e 0 or Γ); (ii) in a larger voltage window ranging from 0 to 200 meV; (iii) for the total calculated I/V curve (from 0 to 1 V). The results of these fits are given in Table 1 together with the reference values Γ t and e 0-t previously obtained. Although the three I/V curves fits are of very good accuracy (R 2 » 1), the associated values e 0-I/V strongly deviate from e 0-t , whatever the bias range considered. The Γ I/V values are at least doubled compared to Γ t . As expected, the conductance G I/V is close to the reference value since it is the fitted quantity. Interestingly, there is an order of magnitude difference between the Seebeck coefficient estimated from the different fitting ranges (S I/V ) and the reference ones (S t ) (see Table 1). The high quality of the I/V curve fits highly contrasts with the poor description of some of the molecular junction properties (e 0 , Γ and S). In the framework of the Transition Voltage Spectroscopy, e 0 can also be estimated in principle as the minimum value in an I/V versus ln(I/V 2 ) plot. [START_REF] Bâldea | Ambipolar Transition Voltage Spectroscopy: Analytical Results and Experimental Agreement[END_REF] This approach is not expected to provide reliable trends when the transmission peak is noticeably shifted with the bias voltage (Figure S3). However, in the case of weakly polarizable organic systems, such as oligophenylene derivatives (see Figure S4), the procedure based on the I/V versus ln(I/V 2 ) plot to evaluate e 0 is applicable. [START_REF] Bâldea | Ambipolar Transition Voltage Spectroscopy: Analytical Results and Experimental Agreement[END_REF][START_REF] Paulsson | Thermoelectric Effect in Molecular Electronics[END_REF] Figure 3. a) Calculated transmission spectrum at zero bias; Lorentzian curves generated from the transmission curve (t), the I/V and the "G+S" fits are given in dotted green, red and black lines respectively; see Figure S3 bias voltages up to 1 V. b) I/V curve obtained from transmission calculations (steps of 0.1 V) and fit of the I/V curve.

Deviations are expected for a large integration voltage window due to the fact that 𝜖 J and Γ are bias dependent properties (Figure S5). The calculated e 0-t varies indeed linearly with the bias (𝜖 J9P (V) = -2.0.10 9R -0.198 V with R² = 0.9914), and Γ t follows a 2 nd order polynomial progression with the voltage change (𝛤 P 𝑉 = 1.4.10 9U 𝑉 V -2.9.10 9W 𝑉 + 3.4.10 9V with R² = 0.9968). Such evolutions revealed in this example are totally omitted in the single-model treatment. It surely induces a failure in obtaining the correct physical properties of a system when using a too large bias voltage window. On the other hand, if the fitting range is too small (|eV| < 𝜖 J9P ), the I/V curves are mainly linear and no meaningful values of the two parameters can be inferred.

A major improvement can be obtained by imposing both the low bias conductance and the Seebeck coefficient of the junction to be recovered with a chosen accuracy (here above 96 %). The procedure adopted is explained in Figure 4. This procedure is referred as the "G+S" method in Table 1. Doing so, the differences against the reference values of Γ and e 0 are strongly reduced, with the right order of magnitude recovered at low bias (Table 1, Figure 3a). This improvement can be rationalized by highlighting that in the I/V fit procedure, a perfect lorentziantype shape of the transmission is assumed. Thus, the more the system deviates from it, the more e 0 and Γ have probabilities to be erroneous even though R 2 is close to 1 (thus G recovered).

Imposing the constraint of also recovering S introduces a tolerance to the deviation from a perfect Lorentzian-shape that significantly improves the extracted parameters. Importantly, although the physical meaning of the parameters is improved, the corresponding I/V curve is apparently less satisfactory, with an R² that significantly deviates from 1. This relates to the fact that deviations are appearing when the linear regime approximation becomes irrelevant, i.e. at higher bias (see Figure S7). The "G+S" procedure can be applied to experimental I/V curves (see Table S3 for applications to data in Reference 34). In conclusion, we have demonstrated that using a Breit-Wigner resonance type model to fit experimental or calculated I/V curves to get an insight into the electronic and transmission properties of molecular junctions can lead to significant errors in the evaluation of the molecular parameters e 0 and Γ. We have shown that the correct position and width of the Lorentzian resonance cannot be reconstructed from the fitted values, even for a case study which presents a quasi-ideal transmission peak shape. The level of accuracy of the fitting procedure in the description of the physics has been strongly improved when considering simultaneously and the Seebeck coefficient of the junction that are both accessible experimental parameters.Erreur ! Le signet n'est pas défini. We hope that our analysis will drive further experimental efforts to improve the reliability of the traditionally done Lorentzian fitting procedures by measuring the Seebeck coefficient in combination with the conductance.

7

 7

Figure 1 .

 1 Figure 1. Simplified scheme featuring a single transporting molecular level of energy e 0 (here the HOMO) coupled by a coupling strength G R to the right electrode and G L with the left electrode. The Fermi energy (E F ) is represented by the dashed line.

A c c e p t e d m a n u s c r i p t

Figure 2 .

 2 Figure 2. Chemical structure of trans-Ru(TMA)(C≡C-C 6 H 4 -SH) 2 (TMA = 1,5,9,13-tetramethyl-1,5,9,13-tetraazacyclo-hexadecane).

  The calculated I/V curve of the Au | [trans-Ru(TMA)(C≡C-C 6 H 4 -S) 2 ] | Au junction has been generated from calculated transmission spectra from 0 to 1 V by voltage steps of 0.1 V. It is represented in Figure 3a. The physical characteristics of the molecular junction can be now deduced by a fitting procedure of the I/V curve, using the single-level model to obtain Γ I/V and A c c e p t e d m a n u s c r i p t

Figure 4 .

 4 Figure 4. Workflow for the calculation of G t /G 0 and S t which yields the (Γ, e 0 ) couple within the "G+S" method. Γ ranges from 0.01 to 0.1 eV and e 0 range from -2 to 0 eV.Restricting the fitting to small voltage segments of the I/V curve could be seen as an alternative since the e 0 and Γ are not supposed to significantly change in each bias window. As shown in FigureS6, this procedure fails in reproducing the right bias dependence of the transmission spectra.

A c c e p t e d m a n u s c r i p t

Table 1 .

 1 Γ (eV), e 0 (eV), S (µV/K) and G (G/G 0 ) obtained by a) application of the single-level method to fit t(E) at each applied voltage (see TableS1); we report here the values averaged over the voltage range, b) fitting of the I/V curve, c) by adding G and S to the fitting procedure. The percentage errors are given in TableS2.

	Bias voltage range (V):	0.0 -0.1 0.0 -0.2 0.0 -1.0
	a) Fit of t(E)	Γ t 𝜖 J9P G t /G 0	0.034 -0.214 0.114	0.034 -0.223 0.115	0.038 -0.311 0.136
		S t	88	86	67
	b) Fit of I/V curve (Eq. 3)	Γ I/V 𝜖 J9Y/[ G I/V /G 0 S I/V	0.169 -0.947 0.114 14	0.105 -0.590 0.114 23	0.165 -0.863 0.129 15
	c) Fit using the "G+S" procedure	Γ "G+S" 𝜖 J9"]7^" G "G+S" /G 0 S "G+S"	0.031 -0.189 0.113 88	/ / / /	/ / / /

ACKNOWLEDGMENTS V.D. acknowledges "Rennes Métropole" for financial support of his scientific stay in Mons. K.C. and V.D. Acknowledge support by the "Grand équipement national de calcul intensif (GENCI)" through HPC resources of CINES and IDRIS (grants 2019/2020-A0080800649/A0060800649). The work in Mons is supported by the Belgian National Fund for scientific research (FR-FNRS). Computational resources have been provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS) under Grant N°.2.5020.11 and by the Walloon Region. J.C. is an FNRS research director. The French Embassy in Berlin is acknowledged for its financial support to the organization of scientific meetings between the authors (Procope structurant 2018).

ASSOCIATED CONTENT Supporting Information

The Supporting Information is available free of charge on the ACS Publications website.

AUTHOR INFORMATION

Corresponding authors

Author Contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

Notes

The authors declare no competing financial interest.

ABBREVIATIONS

TMA, 1,5,9,13-tetramethyl-1,5,9,13-tetraazacyclohexadecane; PF, Power Factor; DFT, Density Functional Theory;