Symbolic Use of Marine Shells and

Mineral Pigments by Iberian Neandertals João ZILHÃO, Diego E. ANGELUCCI, Ernestina BADAL-GARCÍA, Francesco d’ERRICO,

Floréal DANIEL, Laure DAYET, Katerina DOUKA, Thomas F. G. HIGHAM, María José MARTÍNEZ-SÁNCHEZ, Ricardo MONTES-BERNÁRDEZ, Sonia MURCIA-MASCARÓS, Carmen PÉREZ-SIRVENT, Clodoaldo ROLDÁN-GARCÍA, Marian VANHAEREN, Valentín

VILLAVERDE, Rachel WOOD, Josefina ZAPATA

Supporting Information Appendix

Supporting Information I: The site of Cueva de los Aviones

Supporting Information II: The site of Cueva Antón

Supporting Information III:

Radiocarbon dating

Supporting Information IV: Analysis of mineral pigments in finds from Cueva de los Aviones

Supporting Information V:

Analysis of mineral pigment samples from Cueva de los Aviones

Supporting Information VI: Analysis of mineral pigments in a Cueva Antón Pecten

Supporting Information VII:

Reference collection of Acanthocardia, Cerastoderma and Glycymeris shells from modern beaches of Murcia and Alicante

Supporting Information VIII:

Perforated bivalves from prehistoric sites of Mediterranean Spain

Supporting Information IX: References

Supporting Information I: The site of Cueva de los Aviones

Cueva de los Aviones is a sea cave located at the base of a natural promontory protecting

the SW entrance to the Cartagena harbor (SI Figs. 1-2). Local bedrock is made up of carbonate rocks belonging to the Lower Alpujárride unit, of Middle-Upper Triassic age (1-2). The cave walls are composed of moderately deformed light grey and grey limestone (sometimes containing small chert nodules) and dark grey dolomite with intercalations of calcareous breccia and fine layers of yellow sandstone and clay. Locally, bedding of bedrock dips W/20º. The Lower Alpujárride structural unit also contains lithotypes such as slate, quartzite and diabase, all of which outcrop at a short distance from the site. The preservation of brecciated deposits and flowstones well outside the roofed area indicates that the cave was much larger in the Pleistocene, extending several meters E/SE of the present drip-line, whose retreat is related to coastal erosion triggered by sea level rise during the Late Glacial and the Holocene.

These erosive processes almost entirely removed the original fill, except for a brecciated remnant preserved against the northwestern wall of the cave, ~4 m³ of which were excavated in 1985 in a two week-long (September 11-26) salvage operation (3-4) (SI Figs. 2-3). The excavation was carried out in 5 cm spits that followed the natural dip of the stratification and with three-dimensional plotting of stone tool and animal bone finds. The extreme cementation of the deposit (explaining its preservation against millennia of sea erosion and repeated impact of strong waves) made it necessary to proceed with chisel and hammer most of the time, inevitably entailing a significant incidence of excavation breakage among the most fragile category of finds, the shells.

The extant succession, described below following criteria outlined elsewhere (5), is composed of slope sediments accumulated in two distinct cycles and resting on a possibly Eemian rock-beach. From top to bottom, three stratigraphic complexes have been recognized: (1) US (Upper Slope Sediment), which survives in the upper part of the 1985 profile and as cemented remnants hanging from the cave walls; (2) LS (Lower Slope Sediment), which corresponds to the excavated archeological sequence; (3) CC (Cemented Cobbles), which outcrops slightly above modern sea level on the NE side of the current cave entrance and is composed of cemented cobbles and pebbles. Correlation with the units recognized during the 1985 excavation is given in SI Table 1, and a stratigraphic column is presented in SI Fig. 4.

Complex US is made of diamict-like limestone and dolomite forming a heterogeneous cemented breccia that contains rare fragments of bones and lithic artifacts with random orientation. It rests on an erosive surface with evidence of post-depositional deformation, and is separated from underlying complex LS by a discontinuously preserved carbonate flowstone. Complex LS is composed, on average, of coarse material (mainly fragments of carbonate rocks) with a variable degree of post-depositional carbonation (usually intense) and poorly recognizable bedding. It dips SE-E with an inclination of 20-25º and has an erosive base, with angular unconformity. Over a thickness of ~3 m, this complex, originally subdivided in six archeostratigraphic levels, comprises ten different units, all of which contain a variable sand fraction formed of angular and subangular grains of the same lithology as the coarser material, with minor amounts of silt and clay (SI Table 2). Complex CC underlies the archeological sequence, and is shaped as a ridge made up of cemented, clast-supported, rounded cobbles of dolomite and limestone, and occasional quartz pebbles.

As the lithology of the fill is identical to that of the cave, a mainly local source is inferred for the bulk of the US and LS complexes. The geometry of these deposits and of the discontinuous flowstones found along the walls indicates that a several meter-thick seaward-sloping talus cone originally filled the entrance to the cave. The apex of that cone would have been located at the base of the passage that connects the rear part of the site with the inner

2

karst, whence came the geological components of the deposit (complemented by direct falls from the cave’s roof and walls). The sedimentary dynamics involved consist mainly of the accumulation of single fragments (scree-like), although mechanisms related to the action of surface-running waters, such as overland-flow and grain-flow, are also responsible for the formation of some of the observed facies (e.g., units LS04 and LS09).

Despite the abundant archeological remains, neither in situ features nor anthropic microfacies were observed in the extant profiles, although a concentration of burnt bones and charcoal (identified as holm oak by J.-L. Vernet, University of Montpellier) is reported from level IV (3) and may have been part of a disturbed combustion feature. The orientation of the artifacts and bones in the different layers is consistent with the orientation pattern of the rock fragments, indicating that all accumulated together with the sediment and by means of the same sedimentary dynamics. As a result of these processes, stone tools and animal remains underwent lateral displacement, and their horizontal redistribution across the entire surface of the cave means that their place of excavation does not necessarily coincide with the actual area of use and discard. Given the morphology of the cave and the overall geometry of the deposit, human occupation is likely to have taken place towards the inner part of the talus cone, whence the remains recovered in the area of the 1985 excavation were eventually displaced by such low-energy, syndepositional geological processes as discussed above.

Although original site reports (3-4) suggested that a “transgressive marine level” could be observed in level V (=unit LS061), the entire LS complex is in fact of continental origin. Moreover, there is no evidence that any of its units could correspond, even if only in part, to the redeposition of pre-Tyrrhenian marine deposits once extant in the cliff face at a higher elevation. Therefore, the marine shells found in the archeological sequence are non-geogenic, and their association with abundant stone tools and mammal bones (of horse, red deer, ibex, rabbit and tortoise) indicates an anthropic origin.

Five Patella shells from levels I-IV of the 1985 excavation (levels V-VI were sterile) have been radiocarbon dated (Supporting Information III). The results for levels I-III (=units LS02-LS05) are in stratigraphic order, indicate accumulation during the ~45-50 ka cal BP (calendar years before present) interval, and suggest correlation of the LS01 flowstone with Greenland Interstadial 12. The fact that, at ~45 ka 14C BP, the results for levels II and III are statistically the same is consistent with the fact that, in our reading of the stratigraphy (SI Figs. 3-4), the base of level II groups with level III to form a single geological unit, LS05. One of the two results for level IV (=unit LS06u), OxA-19312, is not inconsistent with this chronology and, if accepted as valid, leads to a Bayesian model (SI Fig. 13) that constrains the deposition of the archeological sequence to the ~45-48 ka cal BP interval, broadly coinciding with the very cold episode Heinrich Event 5. However, the mid-point of the uncertainty interval of this level IV result is younger than that for levels II and III, which, given the challenging nature of radiocarbon dating in this time range, could reflect undetected, residual contamination. In this case, OxA-19312 would be a minimum age only. In fact, the deposition of level IV (=upper part of unit LS06) may well significantly predate that of level III, from which it is separated by a noticeable discontinuity (the base of the overlying LS05 unit features common carbonate concretions and has a clear lower boundary).

The other sample from level IV (OxA-20906; ~42.5 ka cal BP) is statistically younger. However, this sample came from square C2, in the seaward row of the excavation grid, where the in situ deposits are covered by a sheet of reworked material derived from the erosion of both the upper part of the LS complex and the lower part of the US complex (SI Fig. 3). As it went unrecognized at the time of excavation, this sheet must have contributed to the collections provenanced to the different archeological levels. Bearing in mind that the OxA-20906 result is younger than the uppermost unit of the LS complex (level I), the simplest explanation for the anomaly is that this C2 sample was in derived position and originally belonged in the US complex. If so, it would place the deposition of the US complex ~42.5 ka cal BP, in the cold

3

stadial comprised between Greenland Interstadials 11 and 12 (SI Fig. 13). Given the topographic location of the US remnants preserved towards the rear of the cave (high along the cave walls), a corollary of this interpretation is that the site would have become entirely filled up by the end of the Middle Paleolithic, in agreement with the fact that no Upper Paleolithic items were observed among the thousands of lithic artifacts recovered in the 1985 excavations.

In all levels, the stone tool assemblages are mostly quartz, suggesting that flint is non-local, but the Levallois method was used in the production of blanks made on both kinds of raw-materials. The absence of flint cores and the high values of the Sidescraper Index (a tool category for which flint was preferentially used) suggest long-distance transport and curation of the finer raw-materials (3-4).

The two perforated Glycymeris shells were found in close association with diagnostic lithics, as noted in the excavation diary, which records their discovery on August 16 and August 17, 1985, during the excavation of layer II of square B1 and in the vicinity of two flint tools, a Levallois point and a Mousterian point (SI Fig. 5). No excavation record exists of the provenience of the perforated Acanthocardia, but in the collections of the Museum of Cartagena it was clearly labeled as coming from level II, in agreement with the published information (4). In the framework of this study, we partially cleaned these shells in order to access the carbonate-coated surfaces around the umbo, for use-wear analysis; they are illustrated in their original condition in SI Figs. 6-7, together with close-up views of the corresponding umbo holes before and after cleaning.

Besides these three previously reported perforated shells, and a Spondylus upper valve with pigment residues identified among the unclassified material in the Museum of Cartagena (Fig. 2), levels I-IV yielded other beach-collected shells of non-food gastropods and bivalves, for the most part coming from levels I and II. The majority are G. insubrica whole valves or fragments thereof (SI Fig. 8), but there are also complete or excavation-broken shells of A. tuberculata and S. gaederopus (SI Fig. 9). The other taxa are illustrated in SI Fig. 10: Callista chione (no. 1, dorsal fragment with umbo); Chama gryphoides (no. 4, dorsal fragment with umbo); Charonia lampas (no. 2, body whorl fragment); Laevicardium oblongum (no. 7, ventral fragment); Pecten maximus (two fragments of a large right valve—no. 3 is a posterior auricle and no. 6 is part of the anterior ventral edge); Thais haemastoma (no. 5, body whorl fragment); and Trunculariopsis trunculus (no. 8, whole shell with a perforation, in all likelihood post-depositional, in the thinner part of the body whorl). This range of taxa includes (and in fact is wider than) that associated with the perforated Nassarius gibbosulus from the early modern human-associated Middle Paleolithic levels of the Near Eastern site of Skhul, which also featured Acanthocardia deshayesii, Laevicardium crassum and Pecten jacobaeus (6).

In terms of ornamental shell find densities, the Aviones values are of the same order of magnitude as those observed in the African MP/MSA sites that yielded significant amounts of Nassarius beads. Considering only the perforated material, the round figures are: for the M1 phase of Blombos, 39 shells over 20 m² and an average thickness of 50 cm (7), i.e., 2/m² or 4/m³; for layer E of Taforalt, 19 shells over 26 m² and an average thickness of 40 cm (8), i.e., 1/m² and 2/m³; for unit II of Aviones, 3 shells over 3 m² and 1 m³, i.e., 1/m² and 3/m³ (and these are minima only, given the many Glycymeris fragments where the umbo area is missing and that originally may have been perforated too).

4

SI Table 1. Synopsis of Cueva de los Aviones succession (the thicker dotted lines indicate discontinuities). Unit Short description Correlation with Montes 1987, 1991 Age

US slope sediment above flowstone OIS-3

LS01 flowstone

LS02 slope sediment, random orientation pattern

LS03 slope, parallel orientation pattern I

conglomerado muy cementado de cantos dolomíticos y tierra negra … estructura de ‘greze litée’

LS04 slope, random orientation pattern

slope, random orientation pattern II conglomerado dolomítico y tierra rojiza

LS05 slope sediment, with a discontinuous carbonate crust at the base (LS05k) III caliche

slope sediment , with few large stones (LS06u) IV microconglomerado areniscoso y tierra rojiza

LS06 slope sediment, with common large stones (LS06l) V (no description)

OIS-3

LS07 slope sediment, strongly cemented

LS08 slope sediment, some parallel orientation pattern

LS09 discontinuous sand intercalation

LS10 slope sediment, no orientation pattern

VI tierra rojiza con algunos cantos dolomíticos OIS-3 or OIS-4

CC rock-beach Eemian

5

SI Table 2. Description of the stratigraphic units in complex LS. Unit Description

LS01 Carbonate flowstone with laminar structure formed of well-crystallised calcite crystals, probably microsparite, strongly cemented. This flowstone is visible at several places along the cave wall, always displaying laminar structure. Its thickness is varied, reaching some 15 cm along the N wall.

LS02 Heterogeneous clast-supported breccia, locally open-work, formed of subangular (with rare subrounded and angular) fragments with random orientation, sometimes parallel to the lower boundary, with clasts from 2 mm to 15 cm (clasts ranging 2-4 cm are the most represented); clasts are composed of white and light gray dolomite, white and light gray limestone, fine calcareous breccia, and yellow or pink weathered sandstone; the matrix is 7.5YR4/2.5 silty-sandy-loam; the sand fraction is fine and formed of angular and subangular grains of dolomite; the carbonation is intense and massive with some laminar structure on top (at the contact with unit LS01); the porosity is low and formed of very fine channels with carbonate hypocoatings; the archaeological material is common and shows random distribution and orientation patterns; the lower boundary is clear, poorly distinct, dipping 25º E; 60 cm thick.

LS03 Fine breccia with moderate sorting formed of subangular and angular (rare subrounded) fragments of the same lithologies as above with good degree of isorientation of the tabular and platy elements, which are parallel to the lower boundary; the size ranges from 2 mm to 3 cm, with an average of about 1 cm; very rare fine (5 mm) rounded pebbles are observed; the matrix is 7.5YR4/2.5 silty-sand; the other features are the same as in unit LS02 but for the archaeological material, frequent; the lower boundary is clear, poorly distinct, dipping 25º to E; 32 cm thick.

LS04 Sandy loam with abundant angular and subangular stones from 2 mm to 6 cm with random distribution and orientation pattern; the matrix is the same as in unit LS03 but some richer in sand formed of angular and subangular grains of local dolomite and limestone; the archaeological material is common; the lower boundary is clear, poorly distinct, dipping 25º to E; 30 cm thick.

LS05 This unit shows the same sedimentary characteristics as the overlying one (unit LS04) except for: the matrix is composed of coarse to very coarse sand with some very fine gravel; some vague stratification, due to the presence of discontinuous fine-gravel partially-open-work intercalations is recognised; common carbonate concretions are found at the base (sub-unit LS05k); the lower boundary is clear, poorly distinct, dipping 25º to E; 25 cm thick.

LS06 Fine breccia with moderate sorting formed of subangular and angular (rare subrounded) fragments of local lithologies with poor (locally moderate) degree of isorientation of the tabular and platy elements, parallel to the lower boundary; the size ranges from 2 mm to 3 cm, with large (max. 20 cm) subrounded and subangular fragments of dolomite, limestone and limestone breccia particularly common at the base of the unit (sub-unit LS06l); the matrix is 7.5YR4/2.5 silty-sand; the archaeological material is frequent; the lower boundary is clear, poorly distinct, dipping 25º to E; 55 cm thick.

LS07 Fine-medium poorly sorted breccia formed of angular and subangular stone fragments from 2 mm to 2 cm, with random distribution and orientation pattern; the is matrix 9YR5/6 sandy-silt, with the sand predominantly in the fine sand sub-class; the carbonation is very intense with strong cementation; no archaeological material is present; the lower boundary is diffuse, poorly distinct; 25 cm thick.

LS08 This unit has the same characteristics as unit LS07 but contains larger stone fragments (max. 10 cm), sometimes with an orientation parallel the lower boundary; no archaeological material is present; the lower boundary is sharp, discontinuous; 10 cm thick.

LS09 Discontinuous thin layer formed of breccia with same characteristics as unit LS07 with 10YR6/5 sandy matrix; no archaeological material is present; the lower boundary is sharp, discontinuous; 4 cm thick.

LS10 Fine clast-supported breccia with occasional stone fragments up to 3 cm, random distribution and orientation patterns; the other characteristics are the same as for unit LS07; the lower boundary is sharp irregular to bedrock or to the complex CC; 20 cm thick.

6

SI Figure 1. Murcia and its Middle Paleolithic. Top. Location of the Region of Murcia in a topographic map of Iberia. Bottom. Location of the Middle Paleolithic sites of Murcia with a stratigraphic or site formation context in a topographic map of the region (elevations in meters).

20 km

7

SI Figure 2. Cueva de los Aviones. Top. Clockwise: site setting, April 2008; the 1985 excavations; the remnant, prior to excavation. Middle. Site plan and profile (3-4). Bottom. View of the cave, April 2009.

A’

A

0 5

N

AA’

m

Middle Paleolithic

brecciated remnant

8

LS02-03 (I)

LS04 (IItop)

LS05 (IIbase-III)

LS06 (IV-V)

CC

flowstone

US

LS07-10 (VI)

rework

ed

A’1

A1

B1 B’1B2

C1 C’1C2

A’1

A1

B1 B’1B2

C1 C’1C2

A’1

A1

B1 B’1B2

C1 C’1C2

A’1

A1

B1 B’1B2

C1 C’1C2

Level I~0.4 m³

Level II~1.1 m³

Level III~0.9 m³

Level IV~1.7 m³

SI Figure 3. Cueva de los Aviones excavation and stratigraphy. Top. View of the remnant in April 2009, with indication of stratigraphic limits (in parenthesis, the archeological level designations used in 1985); the small yellow ruler at the center measures 20 cm. Bottom. The 1985 excavation grid with indication of the areas and volumes affected, per recognized stratigraphic unit.

9

SI Figure 4. Cueva de los Aviones stratigraphic column. A. distribution of archeological finds as observed in the remnant (B=bone fragments, C=charcoal fragments, L=lithic artefacts, S=shells). B. stratigraphic column (the width is proportional to the grain size of the unit’s matrix; C=clay, Si=silt, Sa=sand, G=gravel). C. units described according to this study (US, LS and CC – stratigraphic complexes; LS01 to LS 10 – units of the LS complex; numbers correspond to the average depth in centimetres recorded in the remnant). D. units defined during excavation (the numbers indicate depth of boundaries in the profile as illustrated in refs. 3-4).

10

SI Figure 5. Cueva de los Aviones finds. Top and Middle. Flint tools (from the excavation’s photo archive). Clockwise: point (level I), sidescraper (level I), point (level II), sidescraper (level II), sidescraper (level III), sidescraper (level IV). Bottom. Pages of the excavation diary noting the discovery of the perforated Glycymeris.

11

SI Figure 6. Cueva de los Aviones level II perforated shells, prior to cleaning for this study. Top.Acanthocardia tuberculata. Middle and Bottom. Glycymeris insubrica.

1 cm

12

SI Figure 7. Cueva de los Aviones perforated shells from level II. The perforations prior to (left) and after (right) mechanical cleaning (preceded by removal of the brecciated clutters in an ultrasound vat). Top.Acanthocardia tuberculata. Middle and Bottom. Glycymeris insubrica. Note, especially in the bottom specimen, the heavy chemical micro-weathering around the perforations, which relates to the formation of the carbonate coatings and prevented the presevation of any use wear evidence.

13

SI Figure 8. Cueva de los Aviones non-perforated Glycymeris insubrica shells. Top. Fragments from level I. Middle. Whole shell from level I (from excavation’s photo archive, missing in the Museum of Cartagena) (left) and fragments from level II (right). Bottom. Whole shell and fragment from level III.

1 cm

1 cm

1 cm

1 cm

14

SI Figure 9. Cueva de los Aviones complete non-food bivalve shells. Top. Upper valve of Spondylus gaederopus (level IV). Middle. Lower valve of Spondylus gaederopus (level I). Bottom. Acanthocardia tuberculata shells from level III (left) and level IV (right; excavation-broken).

1 cm

15

SI Figure 10. Cueva de los Aviones non-food shells. 1. Callista chione (level I). 2. Charonia lampas (level IV). 3. Pecten maximus (level III). 4. Chama gryphoides (level I). 5. Thais haemastoma (level II). 6. Pecten maximus(level III). 7. Laevicardium oblongum (level IV). 8. Trunculariopsis trunculus (level III).

1

2

4

5

6

78

3

1 cm

16

Supporting Information II: The site of Cueva Antón

Cueva Antón is a rockshelter excavated into the base of an E-W, 25-30 m high, Eocene

limestone escarpment located towards the tail end of the La Cierva reservoir, on the Mula river (SI Fig. 11). Salvage work undertaken in 1991 exposed a >4-m-thick sequence, at the base of which Middle Paleolithic levels were identified (9). After two seasons (2007-08), new excavation work has also exposed Middle Paleolithic occupations in the uppermost units.

In the areas currently under investigation, the Antón deposits can be divided in four main geoarcheological complexes: DD (Dam Deposits), made up of fine material with some coarser intercalations, and accumulated over the last decades at times when the level of the La Cierva reservoir raised above the base of the shelter’s overhang, fully submerging the site; TL (Transitional Layers), formed of disturbed layers of uncertain age found to the north of row 18 of the grid in intermediate position between the DD deposits and the underlying Pleistocene sediments; AS (Archaeological Succession), formed of a number of superposed alluvial sequences featuring significant lateral variation and distinct sedimentary facies, and including intercalations of slope material, particularly against the back wall and especially so in its upper part (SI Fig. 12); FP (Fine Palustrine), a fine organic sediment forming the base of the exposed succession.

Geomorphologically, the AS complex can best be described as a fluvial terrace created from an alluvial sequence whose sheltering under an overhang limited the impact of post-depositional modifications and soil formation processes. Burrowing features created by rabbits and small carnivores, a major cause of disturbance in all cave and rockshelter sites of Mediterranean and west Atlantic Iberia, are conspicuously absent from the 1991 profiles and have not been observed in current excavation work. Where the uppermost levels of the AS complex are concerned, these observations are consistent with the fact that the abundant rabbit bone component of the deposits is almost exclusively formed of juvenile remains bearing traces indicative of accumulation by eagle-owls (and individual, intact regurgitation pellets have even been recovered in the finer, silty-loamy units). From a taphonomic perspective, the sequence is therefore pristine, with no evidence for vertical post-depositional dislocations and with only limited, horizontal syndepositional displacement of finds having occurred in the coarser levels (those made up of fine alluvial sands or of cm-size cryoclastic wall debris).

Documenting the shifting location of a diverse range of valley bottom environments over the time of accumulation (river channels, gravel bars, sand beaches, bogs, etc.), 48 different units, grouped in five subcomplexes, are currently recognized within the 2-3 m spanned by the AS complex (SI Table 3). Attempts at radiocarbon dating its base have so far failed due to the insufficient yields of the charcoal samples used, but a consistent chronology exists for the upper part, above an erosive unconformity at the base of level II-m. This level corresponds to a gravel/sand bar accumulated at a time when the Mula river ran through the shelter, and the overlying sand beach (level II-l) yielded characteristic sidescrapers and cores for which we have a terminus ante quem of ~43.5 ka cal BP—the age obtained for overlying level II-h/i, an archeologically sterile massive silt deposit accumulated by decantation in the framework of a subsequent episode of low-energy inundation of the site. Carbonate-incrusted level II-d separates the similarly sterile alluvial units that overlie II-h/i from the uppermost archeological occupation, which is contained in level I-k. This unit is a clast-supported breccia formed of small angular limestone debris with a clayey silt matrix and has been dated to ~32.9 14C BP (~37.4 ka cal BP) by a pine charcoal sample pretreated with the ABOx-SC technique (Supporting Information III).

In the basal units of the AS complex, the archeological levels correspond to well-preserved, single-event Mousterian occupations organized around hearth features; stone tools are

17

abundant (SI Fig. 12), and the bones, often cut-marked, are of large herbivores. In the uppermost units (II-l and I-k), however, finds are scarce, suggesting sporadic and highly ephemeral visits only, but, technologically and typologically, the lithics are of Mousterian affinities (SI Fig. 12).

Where level I-k is concerned, the handful of artifacts (including the Pecten shell) was recovered in close association with the dated charcoal samples (Supporting Information III), and these dates place the human occupation represented therein towards the end of the period of late persistence, in Iberian regions located to the south of the Ebro drainage, of a Neandertal-associated Middle Paleolithic (10), which, at Gorham’s Cave (Gibraltar) and Gruta da Oliveira (Portugal), is well documented until ~32 ka 14C BP. Assignment of the level to the latest Middle Paleolithic is further supported by the fact that its characteristics fall outside what would be expected in a context of the regional Upper Paleolithic (for which, moreover, the earliest reliable dates are, at present, <30.5 ka 14C BP). In fact, sporadic occupations of the kind seen at Antón are characterized, in the Upper Paleolithic of SW Iberia, and this from its earliest manifestations, by the discard of endproducts of the chaîne opératoire (bone and stone points, microlithic barbs, and unretouched blade and bladelet blanks) that remain conspicuously lacking in level I-k, despite >3 m³ of it having already been excavated.

SI Table 3. Stratigraphic layout of complex AS of Cueva Antón.

Subcomplex Short description Base Stratigraphic span Archeology Age

AS1 upper part, with slope/ wall inputs and fine alluvial

paraconformity I-g (and unnamed units above) to II-c

I-k (artifacts)

I-k: ~31.1 ka 14C BP

AS2

mainly alluvial sediment, forming at least three minor cycles

erosive unconformity II-d to II-m II-l

(artifacts) II-i: ~39.6 ka 14C BP

AS3

mainly alluvial sediment, forming at least three minor cycles

erosive unconformity II-ñ to II-t — OIS-3

AS4 sand layers preserved in West profile of squares L21-L22

paraconformity II-ø — OIS-3

AS5

mainly alluvial sediment with a poorly developed buried soil on top, forming at least four minor cycles

paraconformity II-u to III-n

II-u/y (artifacts) III-b/d, III-i/j (artifacts, features)

OIS-3

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SI Figure 11. Cueva Antón. Top. The La Cierva dam and reservoir, April 2009 (the circle indicates the location of the rockshelter). Middle. View of the excavation at the end of the September 2008 field season. Bottom. Site plan and grid, with indication of the excavated areas.

Nm

Extant profiles

2007 geological trench2007-08 archeological trenches

1991 Trench 1

1991 Trench 2

Elevation of exposure of the 1991 “unit III” deposits

JKL22

21

20

5 m +4

+2

0

+3 +5 +7

-2

-4-6

0

19

SI Figure 12. Cueva Antón. Top. Flint artifacts from level I-k; left to right, centripetal core on flake blank, denticulate and splintered piece. Middle. Flint sidescrapers from level III-f. Bottom. East profile of the J/17-19 squares, with indication of the stratigraphic units recognized in the AS complex and of the age of dated levels.

II-e

II-ñ

II-p II-r

II-q

II-u

II-m

II-l

II-k

II-i

I-k

~43.5 ka cal BP

~37.4 ka cal BP

J>I17 J>I18 J>I19

— 218 cm

[from Martínez et al., 1991: Fig. 8]

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Supporting Information III: Radiocarbon dating

All radiocarbon dates in this paper were produced at the Oxford Radiocarbon Accelerator

Unit (ORAU), University of Oxford, and were funded by the ORADS-NERC programme. Two different materials were dated: marine shell from Cueva de los Aviones and charcoal from Cueva Antón. The charcoal dates from Cueva Antón reported here come from samples piece-plotted at the time of excavation. They were identified to tree species or wood type—using reflected light microscopy, scanning electron microscopy (SEM), and a reference collection—at the Department of Prehistory and Archeology, University of Valencia.

Cueva de los Aviones Five samples of the limpet Patella ferruginea were selected from the Museum of Cartagena

as suitable for dating. Three samples (AVI-1 to AVI-3) come from the three uppermost archeostratigraphic units, I, II and III, and two (AVI-4 and AVI-5) from unit IV.

All shell samples were cleaned using an air-abrasive system with aluminium oxide until the surface was removed and the inner parts of the exoskeleton were exposed. A small fragment of the carbonate was sawn off and crushed in an agate mortar and pestle to a fine powder. Since limpets are mostly composed of calcite, the stable polymorph of CaCO3, X-Ray Diffraction for the investigation of mineralogical changes in the carbonate matrix was not considered necessary.

Approximately 30 mg of powdered sample was placed in a side-arm (Rittenberg) glass tube and was reacted with 5 ml of 80 % phosphoric acid (H3PO4) for 12 h at 60 ºC, under vacuum. The CO2 evolved was extracted through a manifold, cryogenically purified and transferred into a glass ampoule. The ampoule was cracked, and the gas passed through an automated elemental analyzer connected to a continuous flow isotope-ratio-monitoring mass spectrometer, where it was further purified. The CO2 was then reduced to graphite with H2 at 560 °C for 6 h, in the presence of 2 mg of a Fe+ catalyst. The graphite was pressed into a target holder prior to accelerator mass spectrometry (AMS).

The raw determinations and sample details are given in SI Table 4. In SI Fig. 13, the radiocarbon results are incorporated into a Bayesian model built with OxCal 4.1.1 (11) and are compared against the Cariaco-Hulu record (12-13) and the GISP2 δ18O record. This is a tentative comparison, rather than a calibration, since there is no accepted international calibration curve for this period as yet. Until the release of INTCAL09 calibration curve, the model here is offered in the interim.

The dates from the lowermost level IV do not agree with the overall model: OxA-19312 is in poor agreement with the rest of the sequence (agreement index = 14%), as is OxA-20906, which we treated as an outlier and excluded from the Bayesian analysis. The reasons behind this level IV anomaly in are unclear, possibly reflecting post-depositional mixing (Supporting Information I).

However, given the difficulties in dating very old samples (>40 ka), the results from Aviones show an acceptable agreement and reflect an accumulation of material around the time of the Greenland Interstadial (GIS) 13 and the subsequent Heinrich Event 5. Interestingly, OxA-20906 seems to fall in the stadial between GIS 12 (Hengelo) and GIS 11, also indicating prevalent cold conditions.

Cueva Antón The identification of the dated specimens is given in SI Table 5. Cold ecology pines—Pinus

nigra (salgareño pine) or Pinus sylvestris (Scots pine)—have a very similar anatomy and can be easily differentiated from other pines when presenting the following features:

21

• in the transverse section of wood, vertical resin canals located in the latewood or in the transition zone between early- and latewood and growth ring boundaries always distinct;

• in radial section, heterocellular rays, parenchyma cells with one, rarely two, large pinoid pits per cross-field, and horizontal tracheids with dentate walls.

Distinguishing between P. nigra or P. sylvestris is often not possible (14), although a useful criterion is that, in Pinus nigra, the early- to latewood transition frequently appears more abrupt. In the case of the K19-5 charcoal from level I-k (OxA-20882), a more precise botanical classification was not possible, despite the use of SEM (SI Fig. 14), due to the significant alteration—fusion of cell walls, high degree of mineralization, and fissures and fractures of the plant tissue. Given the biogeographic situation of Cueva Antón, this charcoal is probably from P. nigra, but we cannot exclude P. sylvestris because nowadays, in Eastern Iberia, the two taxa occasionally co-occur.

Two radiocarbon pre-treatment methodologies, ABA (Acid-Base-Acid) and ABOx-SC (Acid-Base-Oxidation-Stepped Combustion), were used to clean the charcoal fragments prior to dating. The former is the standard technique used in most laboratories (15-17). Whilst this is sufficient to remove contamination from the majority of young samples, it has been shown to produce inaccurate ages for some samples dating to >30,000 years ago. ABOx-SC more effectively removes contaminants in samples of this age, but this more rigorous technique requires around 100 mg of well preserved charcoal (18-19). At Cueva Antón, however, much of the charcoal is small and poorly preserved: only three of the 11 samples treated with ABA survived the treatment to produce a date. Therefore, with the exception of sample E20-1, which was treated only with ABOx-SC due to its excellent preservation and large size, all charcoal fragments were first treated with ABA. Subsequently, one sample, J19-7, which was large enough, was also dated with ABOx-SC to examine whether the ABA treatment was able to effectively remove contaminants from charcoal at this site.

During the ABA treatment, the charcoal was sequentially washed at 80 °C in 0.5 M HCl (30 minutes), 0.2 M NaOH (30 minutes, replacing the alkali until excess humics were no longer removed), and 0.5 M HCl (up to 1 hour) (15). ABOx-SC involved washing the charcoal at room temperature in concentrated HCl (1 hour), 1M NaOH (30 minutes, replacing the alkali until excess humics were no longer removed), 0.1M K2Cr2O7/2M H2SO4 (20 hours at 60 oC). After freeze drying, the charcoal was combusted in a sealed evacuated tube with CuO at 630 oC for 2 hours. Between each step in the wet chemistry of both techniques the charcoal was rinsed three times in ultrapure MilliQ™ water or until humics were no longer removed. The products were then combusted, graphitized and measured in an AMS (15-17).

The carbon content and δ13C values of the three ABA samples are within the expected limits for charcoal, although these indicators are relatively insensitive to contaminants. The ABOx-SC date for the sterile deposits capping the Mousterian occupation (level I-i) is modern in age, while that for one of the level I-k samples (J19-7) shows that the ABA result for that same sample is rejuvenated by a couple of millennia (SI Table 5). The other ABA result for level I-k (sample K19-5) should therefore be treated as a minimum age only. The same applies to the ABA result for level II-h/i (sample N20-2)—since we cannot exclude that it is similarly rejuvenated, the ~39.6 ka 14C BP date obtained for this level should be treated with caution until confirmed by ABOx-SC.

The ABOx-SC result for level I-k has been compared to the two high resolution calibration records available for this period—Cariaco-Hulu (12) and Fairbanks et al.’s (20)—within a Bayesian model in OxCal (SI Fig. 13). Given the plateau that exists in both curves ca.33-35 ka 14C BP, the comparison places the final Mousterian at the site within a wide interval centered around 37.4 ka cal BP, during GIS-8 or in the cold stadials on either side of it. A date within one of these stadials, or within the minor cold oscillations recorded towards the end of GIS-8, is supported by the texture of the deposit, which includes abundant cryoclastic wall debris,

22

indicating deposition under cold and dry conditions—in agreement with the presence of Pinus nigra/sylvestris in a charcoal assemblage where the predominance of Juniperus sp. (associated with Ephedra sp. in levels II-l and II-u, further down in the stratigraphy) suggests an open, steppic landscape with scattered mountain pine stands.

SI Table 4. Radiocarbon dates on limpet shells (Patella ferruginea) from Cueva de los Aviones. Sample Level Square OxA Date BP +/- δ13C

AVI-1 I A1 19310 43290 390 3.01

AVI-2 II B1 19311 45000 450 2.69

AVI-3 III B1 19390 45150 650 0.16

AVI-4 IV A1 19312 42200 360 3.27

AVI-5 IV C2 20906 38150 350 1.61

SI Table 5. Radiocarbon dates on wood charcoal from Cueva Antón. Sample Species Level OxA Date (BP) +/- %Yld %C δ13C Treatment

E20-1 Pinus halepensis I-i 20115 98 23 12.6 75.4 -22.5 ABOx-SC

J19-7 Pinus sp. I-k 20881 31150 170 26.9 63.4 -24.0 ABA

21244 32890 200 12.1 (*) 88.4 -22.3 ABOx-SC

K19-5 Pinus nigra type I-k 20882 31070 170 13.8 61.3 -23.4 ABA

N20-2 Juniperus sp. II-h/i 18672 39650 550 21.1 60.1 -22.3 ABA

(*) this value is estimated, as only approximately half of the sample that remained after the wet chemistry was precombusted.

23

SI Figure 13. Bayesian modeling of radiocarbon dates. Top. Cueva de los Aviones, on Patella ferruginea shells. Bottom. Cueva Antón level I-k, on charcoal from Pinus sp.

24

SI Figure 14. SEM images of the Cueva Antón charcoal sample K19-5 (level I-k). The different views show features that are diagnostic of the wood anatomy of Pinus nigra and Pinus sylvestris (photos: E. Badal-García).

Transverse and radial section (x500)

Tangential section with a ray and vertical tracheids (x1000)

Radial section with one large pinoid pit per cross-field; ray with tracheid (x1000)

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Supporting Information IV: Analysis of mineral pigments in finds from Cueva de los Aviones Pigment residues identified in two shells and a bone fragment from Cueva de los Aviones

were analyzed for identification of the minerals and properties of the pigmentatious masses, using SEM-EDS (Scanning Electronic Microscopy with an Energy Dispersive Spectrometer) and Raman spectroscopy, at the Research Center in Archeological Applications of Physics, University of Bordeaux 3.

The pigment in a Glycymeris shell The perforation in one of the umbo-perforated Glycymeris insubrica shells from Cueva de

los Aviones kept at the Museum of Cartagena was cluttered by carbonate-cemented sediments (Supporting Information I; SI Figs. 6-7). In the process of removing the carbonate coating directly adhering to the inner surface of the shell, near the umbo, red particles were observed, collected and submitted for analysis.

Elemental analyses were carried out by SEM/EDS. The microscope was a JEOL 6460 LV. The low vacuum system allows the imagery and analysis without specific preparation (coating) of the sample. An EDS Oxford INCA 300 spectrometer is coupled to the SEM. The powder sample is placed on adhesive carbon disks.

Due to the porosity and low conductivity of the Cueva de los Aviones powder sample, the qualitative analyses were made in low vacuum mode (15Pa), with an acceleration voltage of 20 kV. The data were processed with the INCA software (Oxford instruments).

Raman spectroscopy was carried out with a Renishaw RM 2000 Raman spectrometer coupled with a confocal Leica DMLM microscope and a CCD detector. The analytical conditions were as follows: wavelength of the laser, 632.8 nm; maximum power, 50 mW; microscope magnification, 50x. The calibration of the spectrometer was done with a Si standard (main band: 520.5 cm-1). The spectra were processed with the GRAMS 32 software.

The SEM/EDS elemental analysis (SI Fig. 15) showed that, globally, the major elements are Si and Ca, although lower concentrations of Al and Fe were also detected. Inside the matrix, some minerals are composed of Si, Al, Na and O, while others are mainly composed of Si and O (probably feldspar and quartz, respectively). More rarely, and locally, we found two different mineral species: some “flakes” composed mainly of Fe and Ti, and some barium sulphate crystals. The provenience of these species (from the original archeological or geological context, or artifacts of the sampling and cleaning procedure) could not be assessed.

Under natural light, the observation of the powder collected while cleaning the shell showed some red particles mixed in a white or pink/white sediment. The Raman analysis of several of these red particles produced the characteristic spectra of hematite, and calcite was detected on the white translucent particles of the sample (SI Fig. 16). No other component was found because the intense fluorescence of some minerals occulted the Raman signals.

In conclusion:

• the powder sample analyzed is mainly composed of calcite, probably mixed with siliceous materials (e.g., feldspar and quartz) whose identification by Raman spectrometry was not possible under the experimental conditions (fluorescence of the sample);

• several dark red particles inside the calcitic matrix are hematite.

The pigment in a Spondylus shell After cleaning of the specimen with an ultra-sound cleaner, a reddish accretion associated

with black particles could be observed under the naked eye adhering to the bottom of the inner,

26

concave side of a Spondylus gaederopus upper valve from Cueva de los Aviones. Analysis under the binocular microscope confirmed that the accretion represented a pigment residue, which was surface-analyzed on the specimen, with neither sampling nor preparation, by SEM/EDS and Raman spectrometry, using the same equipment and operational parameters described above for the Glycymeris shell. Identification of the Raman spectra used published sources (21-23).

Under SEM/EDS analysis (back-scattered electrons mode), the red-colored areas did not contrast with the rest of the shell as much as required to allow for precise emplacement, except for the clearly accretionary scale in area a. of SI Fig. 17. In global analysis, this scale is mostly iron. Calcium predominates in the surrounding shell surface (where, however, iron occurs in a significant percentage, some times >10%), and the shape of the crystals, identified as calcite by Raman spectroscopy, suggests recrystalization. Raman spectroscopy also shows that the iron-rich red matrix of this scale is lepidocrocite (γFeOOH, an iron hydroxide). Under greater magnification, components in several shades of yellow, orange and red can be observed, but no other compound besides the red to brown lepidocrocite could be identified. Black and light inclusions were also observed in the scale’s matrix by SEM-EDS analysis. Some are mostly iron, calcium and magnesium; given the geological context, these last two elements are probably dolomite (CaMg(CO3)2), but inclusions rich in iron, or iron and sulfur, also exist. Raman spectroscopy shows that most black inclusions present the characteristic spectrum of “carbon black”—a category of potentially varied origin, e.g., wood charcoal, lampblack, bone or ivory charcoal (24)—but hematite and pyrite (FeS2) were also identified.

Visually, both the dolomite and the black inclusions seem to constitute an integral part of the pigmentatious mass. Conceivably, the dolomite and charcoal could represent post-depositional additions gained from the burial environment. However, this is unlikely, because, according to the excavation reports, only levels III and IV had any charcoal—none was recorded in level II, whence the shell comes, and detailed inspection of the profile corroborated these field observations (SI Fig. 4). Moreover, the hematite and pyrite inclusions present fresh breaks. Despite the non-homogeneous distribution of the inclusions, these facts suggest that the pigmentatious mass corresponds to a red base primarily made up of lepidocrocite to which were added, for binding or effect, ground elements of different origin and darker color—charcoal, pyrite and hematite.

Black and dark red inclusions also exist outside the red-colored areas of the shell, some of which could also be analyzed by SEM/EDS and Raman spectroscopy. In area b. of SI Fig. 17, hematite, “carbon black” and pyrite could be identified (SI Fig. 18; nos. 2 and 5, no. 3 and no. 1, respectively) but the composition of one of the grains (SI Fig. 18; no. 4), rich in iron and featuring poorly defined banding, remains unknown.

SEM/EDS analysis of a white streak adjacent to the red-colored accretions (area c. of SI Fig. 17) revealed a very strong concentration in calcium, and Raman spectroscopy identified calcite (SI Fig. 19). Under SEM/EDS, calcium was shown to predominate in the red areas in direct contact with the streak, although iron percentages approached 10% in these areas; however, no component other than calcite could be detected by Raman spectroscopy.

In a larger black inclusion analyzed by SEM/EDS (area d. of SI Fig. 17), Si and Al predominate, but Raman spectroscopy further identified “carbon black” (SI Fig. 19). This presence may explain the color of the inclusion, but the other elements raise the possibility that it corresponds to an unidentified compound, one whose association with the shell may either relate to the object’s colorant-related function or represent post-depositional accretion of a substance present in the immediate burial environment.

Two inclusions that could only be analyzed by SEM/EDS are rich in calcium and magnesium, in one case, and rich in sulfur and iron in the other. They probably correspond to dolomite and pyrite, respectively.

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Except for the white streak, which is superimposed on the pigmentatious mass and probably represents a post-depositional precipitate, the carbon black, dolomite, pyrite and hematite accretions scattered around the scale in area a. of SI Fig. 17 are probably degraded residues of the same mass. This interpretation probably pertains as well to the pink/red staining of the areas of the shell adjacent to those where pigment was detected and where Raman spectroscopy obtained an iron signal.

In conclusion ( SI Table 6):

• iron oxides (lepidocrocite and hematite) responsible for the red color of the accretions observed are indeed deposited on the shell;

• other components—carbon black, pyrite, dolomite—exist in the pigmentatious mass analyzed, as well as in smaller accretionary clusters dispersed around it.

The pigment in an ancillary metatarsal of horse Under the binocular microscope, small orange particles were observed in the tip of a broken

ancillary metatarsal of horse (SI Fig. 20). This part of the bone was analyzed by SEM/EDS and Raman spectroscopy, with the equipment and operational parameters described above.

Under SEM/EDS, the lighter areas were identified as post-depositional barium sulfate accretions, while the remainder of the bone’s surface appears almost entirely covered by deposits that are for the most part made of calcium carbonate. Two areas where orange particles are readily apparent under the binocular microscope were the object of a finer analysis. On area a., only carbon-rich (organic matter), silicium-rich (quartz?) and calcium-rich (calcite?) particles could be detected. Besides these components, area b. also showed the presence of copper and zinc particles, probably contaminants resulting from the metal tool used to scrape the carbonate coating in order to access the bone surface. No particles were detected that could correspond to the orange material.

Raman spectroscopy was attempted but, because of the small size of the colorant particles and the high fluorescence of the sample, unsuccessfully.

SI Table 6. Compounds identified in accretions on the inner side of a Spondylus shell from Cueva de los Aviones. Shell area

SI Fig.

Elemental analysis (SEM/EDS)

Compound analysis (Raman spectroscopy)

Red to yellow pigment scale 17 Fe Lepidocrocite

White/pink areas adjacent to the scale 17 Ca, Fe Pigment-stained calcite

Inclusions

• light 17 Ca, Mg, Fe Unknown

• black 18, 19 C, Si, Al Carbon black + unidentified alumino silicate

• black 18 Fe, S Pyrite

• dark red to black 18 Fe Hematite

White streak 19 Ca Calcite

Red areas adjacent to the streak 19 Ca, Fe Pigment-stained calcite

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FeFe FeNa KMg CaC

Al

Ca

O

Si

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5keV Pleine échelle 8684 cps Curseur: 0.015 (2173 cps )

SI Figure 15. SEM/EDS global analysis of the powder collected while cleaning the breccia-cluttered umbo perforation in a Cueva de los Aviones Glycymeris shell. Top. EDS spectrum: major elements are Si and Ca; minor elements are Al, Fe, with very small amounts of Na, K and Mg. Middle. Back-scattered electrons SEM image showing a probable feldspar (in the circled area) and flakes composed of Fe and Ti. Bottom. Magnification of the flakes (left) and the barium sulphate crystals (bright acicular elements) (right).

29

SI Figure 16. Raman spectroscopic analysis of particles in the powder collected while cleaning the breccia-cluttered umbo perforation in a Cueva de los Aviones Glycymeris shell. Top. Microscope image and Raman spectrum of a red particle (laser power: 5mW; acquisition time: 60s); the bands at 1330, 617, 506, 412, 295, and 226 cm-1 correspond to hematite; in the databases, the 666 cm-1 band is attributed to either hematite or magnetite but its intensity and occurrence in all our spectra allows the attribution to hematite in this case. Middle.Microscope image and Raman spectrum of a white particle (laser power: 5mW; acquisition time: 10s); the bands at 1086, 714, 284 and 155 cm-1 correspond to calcite. Bottom. Microscope images under natural light of the sample showing red, translucent white and pink/white mineral elements.

226295

412

617

666

1330

506

140 340 540 740 940 1140 1340

Ram

an In

tens

ityRed mineral

(hematite)

Wavenumber (cm-1)

Wavenumber (cm-1)

1086

714284155

140 340 540 740 940 1140 1340

Ram

an In

tens

ity

White mineral(calcite)

30

d.

c.

b.

a.

SI Figure 17. Pigment residues in a Spondylus shell from Cueva de los Aviones. Top. Binocular microscope photo indicating the different areas analyzed. Middle. SEM (back-scattered electrons mode) image of the red scale in area a. (left) and detail of edge of the scale and adjacent shell surface indicating elemental compositions in three areas (1. Ca, Mg, Fe; 2. Fe; 3. Ca) (right). Bottom. Raman spectrum and microscope image of the scale’s red matrix, showing the characteristic bands of lepidocrocite (main bands: 251, 381, 533, 647 and 1319 cm-1).

200 400 600 800 1000 1200 1400Wavenumber (cm-1)

Ram

an In

tens

ity

1319647533

381

251

Red matrix(lepidocrocite)

1

2

3

31

1324

429

375

340

180 380 580 780 980 1180 1380

Wavenumber (cm-1)

Ram

an In

tens

ity

Black inclusion(pyrite)

1328

668

616506

412

293227

180 380 580 780 980 1180 1380

Ram

an In

tens

ity

Wavenumber (cm-1)

Dark red inclusion(hematite)

SI Figure 18. Pigment residues in area b. of a Spondylus shell from Cueva de los Aviones. Top. SEM (back-scattered electrons mode) image; the indicated compounds (1. pyrite; 2. hematite; 3. carbon black; 4. unknown; 5. hematite) were identified by Raman spectroscopy. Middle. Raman spectrum and microscope image of a black inclusion identified as pyrite (main bands: 340 and 375 cm-1). Bottom. Raman spectrum and microscope image of a dark red inclusion identified as hematite (main bands: 227, 293, 412, 506, 616, 668 and 1328 cm-1).

1

2

3

4

5

32

Black inclusion(carbon black)

16041352

200 700 1200 1700

Wavenumber (cm-1)

Ram

an In

tens

ity1084

153

206

135 335 535 735 935 1135 1335

Wavenumber (cm-1)

Ram

an In

tens

ityWhite mineral(calcite)

SI Figure 19. Accretions in areas c. and d. of a Spondylus shell from Cueva de los Aviones. Top. Raman spectrum and microscope image of the white streak in area c., which is calcite (main bands: 153, 206 and 1084 cm-1). Middle. Raman spectrum and microscope image of a large black accretion (area d.) identified as carbon black (main bands: 1352 et 1604 cm-1). Bottom. SEM (back-scattered electrons mode) images of the white streak, area c. (left) and the large black accretion, area d. (right).

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b.

a.

2

1

SI Figure 20. The orange-dotted tip of an ancillary metatarsal from Cueva de los Aviones. Top left. Binocular microscope photo with indication of the areas with orange particles that were analyzed. Top right.SEM (back-scattered electrons mode) image of the bone tip, with indication of the different types of coatings identified (1. barium sulphate; 2. calcium carbonate). Bottom. SEM (back-scattered electrons mode) image of the areas with orange particles—area a. (left) and area b. (right); the dark grey particles look like organic matter and the light ones like calcium or silica; bare bone appears white in the right hand image.

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Supporting Information V: Analysis of mineral pigment samples from Cueva de los Aviones During the 1985 excavation of Cueva de los Aviones, several lumps of colorant material

were recognized and collected in levels I, II and III of the archeological sequence (25; SI Fig. 21). We found samples thereof alongside the site’s faunal and lithic collections kept in the Museum of Cartagena, with clear provenience identification (to site, level and grid unit). From each sample, we extracted two subsamples of identical size. Given the destructive nature of the procedure, the even-numbered subsamples were kept as backup and the odd-numbered ones were submitted to X-Ray Diffraction (XRD) analysis in the Department of Agricultural Chemistry, Geology and Soil Science of the Faculty of Chemistry, University of Murcia.

X-Ray Diffraction (XRD) analysis allows a semiquantitative estimation of the mineralogical composition of the samples and was carried out using Cu-Kα radiation with a PW3040 Philips Diffractometer. The X-powder software (26) was used to analyze the X-Ray diffraction diagrams obtained by the crystalline powder method. The powder diffraction file (PDF2) database was used for peak identification, taking into account that the determination of minerals from soils by XRD analysis is not accurate below a limit of 5% of the total weight in a sample (depending on the crystallinity of individual minerals). The results are given in SI Table 7 and the corresponding spectra in SI Figs. 22-23. The yellow colorants are primarily natrojarosite, while nontronite, hematite and goethite were identified in the red ones, and siderite on both types.

Cueva de los Aviones is adjacent to one of the main mining districts of SE Spain, La Unión, where stratabound sulfide deposits are found in carbonate sequences of the Nevado-Filábride and Alpujárride complexes (27-28). These complexes consist of a series of superimposed thrusting mantles of Alpine age, affected by upward metamorphism. After a very strong erosion phase, a transgressive Neogenous series was deposited on these mantles. Subsequently, there was a phase of strong fracturing followed by volcanic phenomena and uplifting, and more recent erosion processes.

This Pb-Zn-(Ag-Sn) district is an excellent example of the interplay between basin formation, normal faulting, volcanism, hydrothermal activity and mineral deposition (29), all synergistically combining to create exceptional concentrations of metals. The Neogene magmatic process is represented by calc-alkaline rocks (andesites, pyroxene and amphibole-bearing andesites and dacites) and alkaline basalts (basanites and olivine basalts). The first is characterized by domes and dykes, with only rare lava and pyroclastic deposits. The domes are typically made up of fragments of volcanic rocks embedded in a matrix of the same composition. Basaltic volcanism is characterized by pyroclastic rocks and small lava flows. Despite their young age, the erupted materials are highly weathered and the volcanic vents are strongly eroded (30). Where these volcanites push up, they constitute the typical cabezos of the area (including the islands of the Mar Menor, a marine lagoon aligned along 70º N), as well as the embankments and domes (aligned 130º N) that intersect the litho-structural levels, including the Miocene.

These volcanites, dacites and andesites (which have been assigned ages of 7 to 11 million years) are affected by strong hydrothermal alteration in the areas where mineral outcrops occur. The processes affect both the volcanic rock and the parent material. Hydrothermal activity related to middle Miocene subvolcanic magmatism was focused along normal faults bounding a graben. Mineralization occurred (i) within a strongly altered zone above the Miocene footwall; (ii) in pebbly mudstone beds where the hydrothermal activity led to dissolution, void formation and mineral deposition; and (iii) in fault breccias along the normal faults that bound the Miocene sediments (27). The primary mineralization of the area was succeeded by a strong secondary transformation process, resulting in the appearance of a large number of secondary

35

minerals, while the supergenic alteration processes affected both the primary mineralization products and the host rocks, as occurs in the nearby mining district of Mazarrón (31). This volcanism process occurred mainly from the Oligocene to the Quaternary along a strip measuring 150x25 km (9000 km2), between Almería (Cabo de Gata) and Cartagena (Manga del Mar Menor). It is known as the “Almería-Cartagena Volcanic Belt” (ACVB) (32) or “Southeast Volcanic Province (SEVP)” (33).

Groutite is a manganese compound, while the other minerals identified in the colorant material analyzed are iron compounds. A local origin can be excluded for the latter, because the catchment of the Aviones karstic network is confined to Triassic dolomite and limestone terrain that went unaffected by the volcanism and hydrothermalism processes discussed above. The walls of the cave, therefore, cannot themselves be the source for the iron sulfides (e.g., pyrite) and the byproducts of their weathering (e.g., natrojarosite) identified in the Aviones samples simply because, in the region, such minerals did not form until some 200 million years after the laying down of the sediments that make up the site’s bedrock. Likewise, the goethite and hematite samples cannot result from the precipitation in the archeological deposits of minerals present in the encasing dolomite and limestone walls because, in these rocks, iron only occurs in trace amounts.

Intercalated lenses of red clay can be observed in the dolomite stratification exposed in the cave walls, and it is therefore conceivable that wall degradation processes contributed the mineral components of these clays to the site’s fill. There is no evidence, however, that such contributions occurred as masses of macroscopic size, as none were recorded in the profiles or during excavation, and the texture of the archeological deposits is that of a coarse sand (SI Fig. 4). So, although provenance from the clay lenses intercalated in the dolomites is conceivable for any iron oxides and hydroxides (e.g., hematite and goethite) found in the sedimentological fine fraction of the Aviones deposit (i.e., in the clay and silt grain size classes), such a provenance can be excluded for the macroscopic-sized colorant samples. For the lepidocrocite identified in a Spondylus shell from level II (Supporting Information IV), however, this is not even an issue, because this mineral is absent from calcareous soils, and the same applies to natrojarosite, which only occurs in sulfidic soils (34).

Since the sampled colorants are not of local origin, they can only represent an anthropic contribution to the Aviones deposits. Potential sources are ubiquitous throughout the ACVB, and the nearest such suitable terrain lies ~3.5 km to the west (around the Cabezo de la Estrella) or ~5 km to the north (across the Sierra de Pelayo) (1-2). However, for jarosite and other minerals of the same family, like the natrojarosite in subsamples 1 and 11, the number of source localities can be narrowed down to a few. These minerals result from the weathering of pyrite and other iron sulfides when and where the latter are atmospherically exposed, which results in the formation of weathering crusts that can also contain secondary byproducts of the process (e.g., goethite and other hydroxides). Thus, the acquisition of pure natrojarosite, as that in subsample 1, requires a source where the parent mineral is of considerable mass as, otherwise, contaminants derived from the weathering of the encasing rock would also be present (35-36). Such quality jarosite can therefore be presumed to come from one of the major outcrops of iron sulfides in the region, whose location is provided in SI Fig. 24. The closest are located in an area ~7 km east of the cave, along the Rambla de Escombreras, across the bay of Cartagena.

Goethite and hematite can also be found beyond the boundaries of the ACVB. On Triassic bedrock especially, small, non-mapped outcrops can exist, because, throughout the province of Murcia, the Triassic features varied marly deposits, in general with a high content in gypsum and other soluble salts, that are, therefore, rather plastic. These deposits lie at the base of the numerous diapirs of the interior of the province (Segura valley and the different Tertiary lacustrine basins), where ophite outcrops occur. The latter are intermediate volcanic rocks that can be associated with hydrothermalism processes resulting in the presence of iron minerals

36

(hematite, magnetite) and, with hydrothermal weathering, in the generation of clays (smectite) and such secondary minerals as iron hydroxides (goethite, lepidocrocite, limonite, etc.). Another potential source for hematite are the clays that result from the degradation of carbonate rocks, in which case quartz and calcite in varying amounts will also be present. Such clays can be found as constituents of the red soils found in the Campo de Cartagena. However, the presence of siderite in all the red-colored samples from Aviones indicates that any potential hematite sources in the Campo de Cartgena area can be excluded because siderite cannot form as a result of soil weathering processes. Therefore, the Aviones hematite- or siderite-based red pigments must come from sources related to post-volcanic hydrothermal processes such as those associated with the diapirs in inland Triassic bedrock or with the littoral Almería-Cartagena Volcanic Belt. The latter are those closest to the site.

In short, the mineral pigment masses sampled during excavation in levels I-III of Aviones are manuports, not natural components of the deposit. A measure of uncertainty remains concerning the exact location of their sources, but the local and regional geology implies transport over distances >3 km for the red pigments and >5 km for at least the yellow natrojarosite.

SI Table 7. Provenience of the pigment samples from Cueva de los Aviones and results of the XRD analysis. Subsamples Square Level Color Subsample analyzed and colorant minerals identified

1 & 2 C1 III Yellow 1 Natrojarosite

3 & 4 C1 (?) III Red 3 Siderite

5 & 6 A1 I Red 5 Nontronite, Siderite

7 & 8 A1 II Yellow 7 Siderite

9 & 10 A1 II Red 9 Goethite, Hematite, Siderite

11 & 12 A1 II Yellow 11 Groutite, Natrojarosite, Parabutlerite

37

SI Figure 21. Cueva de los Aviones pigments. Top. Page of the excavation diary recording the presence of pigments in level III, grid unit B1. Bottom. Pages of the field books from grid units A1 (left) and C1 (right) recording the presence of yellow and red pigments in levels I and III, respectively.

38

5 10 15 20 25 30 35 40 45 50 55 60 65 70 75

0

68

136

204

272

341

409

477

545

613

681 Counts

2-theta

Natrojarosite

Source of subsample 1 [Level III, square C1]

2 mm

5 10 15 20 25 30 35 40 45 50 55 60 65 70 752-theta

0

66

132

198

264

330

396

462

528

594

660 Counts

Source of subsample 5[Level I, square A1]

SideriteNontronite

5 m

m

SI Figure 22. Cueva de los Aviones. XRD pigment analysis. Top. Subsample 1; all peaks are natrojarosite. Middle. Subsample 3; other peaks are quartz, calcite, dolomite and muscovite. Bottom. Subsample 5; other peaks are anorthite, calcite and muscovite.

Siderite

5 10 15 20 25 30 35 40 45 50 55 60 65 70 752-theta

0

67

134

201

268

335

402

469

536

603

670 Counts

Source of subsample 3 [Level III, square C1]

39

SI Figure 23. Cueva de los Aviones. XRD pigment analysis. Top. Subsample 7; other peaks are quartz, calcite and muscovite. Middle. Subsample 9; other peaks are quartz, calcite, muscovite, dolomite and sanidine. Bottom.Subsample 11; other peaks are quartz.

5 10 15 20 25 30 35 40 45 50 55 60 65 70 752-theta

0

65

129

194

258

323

388

452

517

581

646 Counts

Siderite

Source of subsample 7[Level II, square A1]

5 mm

5 10 15 20 25 30 35 40 45 50 55 60 65 70 752-theta

0

63

126

189

252

316

379

442

505

568

631 Counts

GoethiteHematite

Siderite

Subsample 9 [Level II, square A1]

5 10 15 20 25 30 35 40 45 50 55 60 65 70 752-theta

0

66

132

197

263

329

395

461

526

592

658 Counts

Natrojarosite

Groutite

Parabutlerite

Subsample 11 [Level II, square A1]

40

SI Figure 24. Cueva de los Aviones. Sourcing of the colorant materials analyzed by XRD. Top.Physiographic map. Bottom. Geological map (same scale). The white triangle represents Cueva de los Aviones, and the black triangle represents Cueva Antón. Two potential source areas exist for the red colorants, the littoral Almería-Cartagena Volcanic Belt and the ophites and associated weathered deposits of the interior diapirs, separated by the Quaternary glacis of the Campos de Cartagena, where siderite cannot occur. The orange dots indicate the major outcrops of iron sulphides whence the pure natrojarosite from level III probably came.

41

Supporting Information VI: Analysis of mineral pigments in a Cueva Antón Pecten

Naked eye and binocular microscopic inspection of an upper valve of Pecten sp. recovered

at Cueva Antón suggested that residues of red/yellow pigment were preserved on one of the sides of the shell. In order to verify these observations and identify the minerals present, non-destructive analyses using X-Ray fluorescence and micro-Raman spectroscopy were carried out at the Institute of Materials Science, University of Valencia.

X-Ray fluorescence (XRF) We used a portable XRF spectrometer with a silver transmission anode and a Si-PIN

semiconductor detector cooled by Peltier effect with a resolution of 170 eV (FWHM @ 5.9 keV). The analyzes were carried out at 30 kV, 3 μA, and with an acquisition time of 180 seconds. The measuring geometry was 45º, with the incident beam collimated at a diameter of 3 mm and directed perpendicular to the sample. The distance between sample and detector was 18 mm.

The internal face of the shell presents a reddish coloration, for which observation under binocular microscope suggested a biogenic cause. The external face presents a whitish coloration and features red/yellow terrigenous deposits that, under the binocular microscope, overlie the surface of the shell. We carried out XRF analysis of one of these accretions (point P01) and compared the results with those obtained by XRF analysis of the shell’s body in areas where it presents both a whitish (point P02) and a reddish (point P03) coloration.

In the fluorescence spectra obtained (SI Fig. 25), the fluorescence peaks related to the constituent materials of the measuring equipment were marked with the label “tube.” The position of the so-called Ca-escape peak, which relates to the presence of this element, was also signaled.

The fluorescence spectra indicate a calcareous matrix (Ca) with impurities of iron (Fe), sulfur (S) and strontium (Sr); the latter is often associated with calcium. The spectra of the calcareous matrix are practically identical in both the whitish and the reddish areas, indicating that the coloration is biogenic. The spectrum of the red/yellow accretion presents an iron fluorescence peak significantly more intense than that of the calcareous matrix. This indicates the presence of an iron oxide compound with an iron concentration higher than that of the shell’s; RAMAN spectroscopic analysis (see below) indicates that goethite (FeO[OH]) is its major component.

The accretionary nature of this mineral deposit is best appreciated in the detail graph at the bottom of SI Fig. 25. This graph represents, on a linear scale, the Ca and Fe fluorescence peaks. In point P01 (the accretion), an increased Fe fluorescence corresponds to a decreased Ca one. This indicates that Fe attenuates the Ca signal in the areas with superficial deposits of iron oxides.

Micro-Raman spectroscopy Micro-Raman spectroscopy was carried out at room temperature, in a backscattering

configuration and using the 514.5 nm line from an Argon laser for excitation. The scattered light was dispersed by a Jobin Yvon T64000 triple spectrometer and detected with a liquid nitrogen-cooled CCD. The typical system spectral resolution was around 2 cm-1.

The laser beam was focused on the sample’s surface using a Leica microscope 100x objective. In order to prevent local heating and transformation, laser power varied from 3 to 14 mW. Recording times ranged from 30 to 300 seconds, with 2 to 10 accumulation scans depending on the sample. Measurements were carried out directly on the sample with no previous preparation of any kind.

42

The Raman spectra in SI Fig. 26 have been corrected for background fluorescence and the base line is shifted for clarity. The identification of blanks and pigments was carried out by comparison with published spectra and available databases.

Red/yellow pigment is visible only on the whitish, external side, where it can be found across the whole surface, with a discontinuous distribution, filling grooves and spilling over adjacent areas. To see whether undetected pigment residues existed also on the internal, reddish side, we obtained Raman spectra from both sides and in different parts of the shell. The areas analyzed are indicated in SI Fig. 26.

The Raman spectrum of the internal (reddish) side shows calcite bands (285, 714 and 1088 cm-1) (37) attenuated by the presence of bands related to the pigments of the shell itself (1019, 1134 and 1301 cm-1), which are carotenoids (38-40). No anthropogenic mineral pigments were detected on this side of the shell.

The different spectra obtained in the three areas with red/yellow pigment that were analyzed show very clearly the presence of bands that correspond to two iron oxides: hematite (α-Fe2O3), responsible for the red color (290, 408, 506, 608 and 642 cm-1); and goethite (α-FeOOH), responsible for the yellow color (215, 272, 386 and 588 cm-1) (22, 41). The final result is a mixture of both pigments, yielding an overall orange hue.

Hematite is the most stable iron oxide. Nevertheless, structural variations from pure hematite, due to the replacement of Fe atoms by other atoms (e.g., Al or OH groups), can be found in nature. These atomic substitutions can cause displacement of the Raman bands (by comparison with those for the well crystallized, pure oxide), due to small variations in the crystalline structure. The Raman bands observed in the analyzed oxides fit those of pigments that were naturally modified and subject to ageing and corrosion processes (41). The same applies to goethite.

No bands around 660 cm-1 were detected. This band, which indicates the presence of magnetite, is known to occur in some spectra, often as a result of the utilization of too much laser power.

Hematite and goethite occur in the La Unión mining district, in the littoral area of the Murcia province, but they can also occur as a result of the weathering of ophites and other volcanics, e.g., fortunites, in diapirs of the interior (see Supporting Information V). Since an outcrop of fortunites is mapped near the town of Puebla de Mula, ~5 km from Cueva Antón, such is the closest potential source for the mineral pigment found on the Pecten shell recovered at the site.

43

3 4 6 70.00

0.01

0.02

0.03

0.04

0.05

Nor

mal

ized

cou

nts

Energy (keV)

P01 red/yellow accretionP02 white (shell’s body)P03 red (shell’s body)

Ca

CaFe

5 10 15 2010-5

10-4

10-3

10-2

10-1

tube

Nor

mal

ized

cou

nts

Energy (keV)

P01 red/yellow accretionP02 white (shell’s body)P03 red (shell’s body)

Ca

Fe

Fe SrS

tube

Ca-

esca

pe

PO1

PO2PO3

SI Figure 25. XRF study of the Cueva Antón Pecten. Top. The shell, with indication of the points where the different spectra were obtained. Middle. The fluorescence spectra. Bottom. Detail of the fluorescence spectra in the areas of the calcium and iron peaks.

44

SI Figure 26. Raman micro-spectroscopic study of the Cueva Antón Pecten. Top. The shell, with indication of the points where the different spectra were obtained. Middle. Results for the internal (reddish) side. Bottom. Results for the external (whitish) side and microphoto (at 100x) of pigment residue.

1350

Ram

an In

tens

ity

150

Internal (red) side[calcite with carotenes]

250 350 450 550 650 750 850 950 1050 1150 1250

Raman Shift (cm-1)

285 714 9771019

1088

1134

1301

150 300 450 600 750 900 1050 1200 1350Raman Shift (cm-1)

Ram

an In

tens

ity

215

272

386

408

588608

10881123

290

642506

External (white) side[mineral pigments]

GoethiteHematite

50 μm

45

Supporting Information VII: Reference collection of Acanthocardia, Cerastoderma and

Glycymeris shells from modern beaches of Murcia and Alicante In order to assess the nature and significance of the perforated bivalve shells from Cueva de

los Aviones and other prehistoric sites of Mediterranean Spain, we assembled a reference collection whose composition and collection criteria are given in SI Table 8. Because of the different purposes involved, we used a set of attributes different and simpler than those in a recent, paleontologically oriented taphonomic study of Glycymeris shells (42). The collection is kept and openly available for analysis at the University of Murcia, Department of Zoology and Physical Anthropology. All measurements were made with a digital caliper, following Claassen 1998 (43); perforation dimensions were measured internally, as the diameters of an ellipse. These measurements and the associated discrete criteria (defined in SI Table 9) are tabulated in a Supporting Data Excel file and summarized in SI Table 10.

Samples 4 and 5 reflect a purely marine catchment. Sample 4 is made up of weathered material and was almost entirely collected in a concentration of 5-10 m radius in Cala Arturo, immediately to the north of the Calblanque beach (Murcia), but also contains a few specimens found along the latter’s dunes. Sample 5 is made up of a very few specimens collected in the intertidal zone of a beach to the west (Playa Parreño), but mostly comes from a back dune exposure and, given small sample size, was not included in the study. These beaches are 23 km due east of Cueva de los Aviones, in a similar geological and geomorphological setting, and yielded bivalve shell assemblages of similar composition to that recovered at the site. All the Glycymeris shells in these samples belong to the G. insubrica species.

Samples 1 and 2 are primarily made up of Cerastoderma glaucum and reflect a mixed estuarine/marine catchment, in agreement with the location of the Guardamar beaches (Alicante), north and south of the mouth of the Segura river. Besides a majority of recent material, these samples may also contain shells of earlier ages derived from submerged Pleistocene or Early Holocene deposits. The shells are for the most part weathered, but display a rather varied surface appearance, from erosion limited to the dorsal edges with near intact crenulated ventral edges to heavy corrosion and thinning of the entire shell (as if bathed in acid); also, a high proportion bear a grey color indicative of post-mortem burial in clay environments deprived of oxygen. In contrast, most Acanthocardia tuberculata specimens are in near-pristine condition, especially the complete ones in sample 3. Another species of the same genus, A. paucicostata, is also represented in the Guardamar samples but in low numbers and, hence, was not considered in the analyzes.

In the G. insubrica sample (SI Fig. 27), 45.8% of the shells preserving the umbo area are perforated, and, with the exception of a dorsally placed hole in a specimen that is both very small (18.2 mm height) and quite thinned, all the perforations are in the umbo. The presence of a perforation is not determined by size, as the height of perforated (36.5±6.9 mm) and non-perforated (37.5±7.2 mm) shells is statistically the same, and there is no correlation (r=0.34) between the size of the shell and the area of the hole (measured as an ellipse), for which the maximum internal diameter is a good predictor (r=0.89) and was therefore used as a proxy (in the preceding as well as in the following discussion, average±standard deviation values are used). The key factor underlying variation in both presence and size of the perforation is weathering stage. The more weathered the shell is, the higher the probability that the umbo will be perforated (stage 4 is an apparent exception only, as it is defined on the basis of different criteria; SI Table 9), and the size of the perforation increases with weathering—for shells where the umbo area was preserved and hole size was measurable, only one stage 1 specimen (1.3%) was perforated, and with a small hole (0.9 mm), contra 63.7% of the material in stages 2 and 3 (hole size, 5.3±2.9 mm) (Supporting Data; SI Table 10, Fig. 28).

46

In the C. glaucum sample (SI Fig. 29), the percentage of perforated shells, mostly below the umbo, is 7%. Only two (0.3%) fall in the “full umbo” category and, in both cases, the shells are small (with heights of 13.3 and 17.5 mm) and the holes narrow (1 and 2 mm, respectively). Eight shells (1.1%), all also rather small (between 9.8 and 18.7 mm in height), feature an “open umbo” perforation with a larger diameter (3.9±1.2 mm). The number of shells with a perforation below the umbo is 40 (5.5%), of which only one is ventrally placed. These shells are larger (20.4±4.9 mm in height), and so are the holes (8.0±3.8 mm). Significantly, 57.5% of the dorsally or ventrally perforated shells display visible exfoliation, a percentage that is similar to that observed among the umbo-perforated specimens (50%) and contrasts markedly with the frequency of the attribute (11.0%) among the non-perforated ones.

It has been argued that, in Cerastoderma, a dorsal or ventral position of the hole is an indicator of anthropic origin because umbo perforations should be the norm in such shells (44). As the Guardamar collection shows, this argument is not valid. The positive correlation between exfoliation and perforation indicates that, in Cerastoderma, perforation occurs naturally as a byproduct of corrosion/decalcification processes, as the examples in SI Fig. 29 well illustrate. That, possibly in relation to burial environment, corrosion rather than abrasion is the main weathering process affecting Cerastoderma shells may also explain why, in this taxon, perforations below the umbo are four times more common than perforations of the umbo (although factors relating to shell geometry and shell texture may also be involved).

In the A. tuberculata sample (SI Fig. 30), the percentage of perforated shells (4.5%) is of the same order of magnitude as that found among C. glaucum, but the number of “full umbo” (three) and dorsal (two) holes is similar. A significant difference between the two taxa is that exfoliation is a rare occurrence (1.8%) in the A. tuberculata sample, suggesting that, in this case, the main weathering process in operation is abrasion rather than corrosion. That a higher energy burial environment pertains for the A. tuberculata shells from Guardamar is corroborated by the fact that the two dorsal holes occur in shells with rather good surface condition and result from shock breaks that entailed loss of a circular area below the umbo, with no subsequent abrasive smoothing of the edges of the perforation. These shells illustrate how entirely natural processes can mimic “direct percussion” and imply (contra refs. 45-46) that perforation by “direct percussion” is not, by itself, a valid criterion upon which to base an anthropogenic diagnosis.

In conclusion, the two types of wear evidence that have been invoked in the literature to support an anthropogenic diagnosis for the perforations seen in shell ornaments—“abrasion” and “direct percussion”—are entirely natural processes too. Therefore, at least where bivalves are concerned, and especially so for the taxa that are most common in archeological assemblages and for which reference material is available (Cerastoderma, Acanthocardia and Glycymeris), our observations imply that natural, as opposed to anthropic, is the null hypothesis for the origin of the perforation, and that a perforation can be deemed anthropogenic only if one of the following conditions applies:

• evidence is produced that a tool was involved in the perforation, e.g., microwear typical of the use of a drill;

• the weathering stage and perforation patterns (size and emplacement) deviate from those seen in natural thanatocenoses, e.g., for Glycymeris, if the hole is large but made on a fresh, unweathered shell and/or away from the umbo;

• the hole is associated with artificial modification of the shell’s geometry, e.g., gouging of the external surface to prepare a perforation in the middle of the shell, as in the Neolithic specimen from Gruta do Caldeirão illustrated in SI Fig. 28 (47).

47

SI Table 8. Collection data for the modern bivalve reference sample. Parameters Sample 1 Sample 2 Sample 3 Sample 4 Sample 5

Date 10-01-2009 02-02-2009 02-02-2009 03-02-2009 03-02-2005

Time 16:15-17:45 13:15-15:15 16:30-17:30 12:00-13:30 14:00-15:00

# of collectors 2 2 2 2 2

Beach Guardamar Guardamar Guardamar Cala Arturo Parreño

Province Alicante Alicante Alicante Murcia Murcia

Geographical coordinates

38°4'58" N to 38°5'53" N

38°6'05" N to 38°6'37" N

38°6'46" N to 38°7'30" N

0°43'33" W to 0°43'53" W

0°45'16" W to 0°45'52" W

Target taxa Acanthocardia Cerastoderma Glycymeris

Acanthocardia Cerastoderma Glycymeris

Acanthocardia Glycymeris

Glycymeris Glycymeris

Collection criteria

Glycymeris, regardless of completeness, plus complete or dorsal Cerastoderma/Acanthocardia (broken ones collected occasionally)

Any and all, regardless of completeness

Any and all, regardless of completeness

Other bivalve taxa recorded

Chamelea gallina, Spondylus gaederopus, Arca noae, Mytilus galloprovincialis, Chama (?) sp., Callista chione, Laevicardium sp. (cf. oblongum), Donax trunculus, Modiolus sp. (cf. barbatus), Tapes decussatus, Eastonia rugosa, Tellina incarnata, Lima inflata, Lima lima, Chlamys glabra, Chlamys varia, Mactra stultorum, Venus verrucosa, Ostrea edulis

Cerastoderma glaucum, Chamelea gallina, Spondylus gaederopus, Acanthocardia sp., Arca noae, Mytilus galloprovincialis, Anomia ephippium, Chama (?) sp.

Gastropod taxa recorded

Patella aspera, Patella caerulea, Fissurella nubecula, Semicassis undulata, Thais haemastoma, Turritella communis, Trunculariopsis trunculus, Aporrhais pespelecani

Patella aspera, Patella caerulea, Patella rustica, Semicassis undulata, Thais haemastoma, Charonia lampas, Cancellaria cancellata, Bulla striata, Acteon tornatilis, Columbella rustica, Calliostoma laugieri, Monodonta turbinata, Nassarius mutabilis, Nassarius sp. (cf. incrassatus or pygmaeus), Nassarius nitidus, Nassarius granum

48

SI Table 9. Definition of discrete attributes recorded in the modern bivalve reference sample. Attributes A. tuberculata and C. glaucum G. insubrica Weathering • Yes/No (Yes, if crenulated edge is

significantly abraded on the ventral side, opposite the umbo; not recorded for C. glaucum)

0. fresh

1. some weathering; hinge teeth and denticulation of ventral margin well apparent

2. significant weathering; teeth and/or denticulation of ventral margin partly erased but both still somewhat apparent in part

3. major weathering; teeth and denticulation of ventral margin (or at least one of the two) completely erased

4. fragment with umbo whose breakage edges were fully regularized/rounded (with no angular breaks) by subsequent abrasion

Sponge holes • Through: if, visibly to the naked eye, there are sponge holes that traverse the shell from one side to the other

• Non-through: if there are sponge holes even if they don't traverse the whole shell

• Absent

• Yes/No (through-holes only)

Exfoliation • Yes/No Not recorded

Predator holes • Yes/No • Yes/No

Bioaccretions • Yes/No • Yes/No

Intactness • Complete: height and length measurable despite small mechanical fractures (if any), reduction in size from living due to abrasion only

• Dorsal: umbo area preserved, losses to mechanical fracture elsewhere, at least one dimension non-measurable

• Ventral: umbo area lost to mechanical fracture, height non-measurable

• Edgeless: fragment comprised of flattish area in the middle of the shell, with all edges rounded and no identifiable area of the shell margin present

Perforation • Full umbo: hole with complete circumference preserved

• Open umbo: hole with break to the inner side

• Ventral: hole closer to the ventral than to the dorsal edge

• Dorsal: hole closer to the dorsal than to the ventral edge

• None: no perforation

49

SI Table 10. Descriptive statistics for the modern bivalve reference sample (all measurements are in mm and given as average±standard deviation). Attributes A. tuberculata (samples 1-3) C. glaucum (samples 1-2) G. insubrica (sample 4) Weathering Stage N = 94

Yes = 22.4%

No = 77.6%

Not recorded N = 705

0 = 0.0%

1 = 17.5%

2 = 27.4%

3 = 50.3%

4 = 4.9%

Sponge holes N = 110

Absent = 96.4%

Non-through = 0.0%

Through = 3.6%

N = 715

Absent = 98.0%

Non-through = 1.5%

Through = 0.4%

N = 705

Absent

or Non-through = 94.3%

Through = 5.7%

Exfoliation N = 110

Yes = 1.8%

No = 98.2%

N = 715

Yes = 14.1%

No = 85.9%

Not recorded

Predator holes N = 110

Yes = 1.8%

No = 98.2%

N = 715

Yes = 0.3%

No = 99.7%

N = 705

Yes = 0.3%

No = 99.7%

Bioaccretions N = 110

Yes = 0.9%

No = 99.1%

N = 715

Yes = 0.6%

No = 99.4%

N = 705

Yes = 0.7%

No = 99.3%

Intactness N = 110

Complete = 54.5%

Dorsal = 45.5%

N = 715

Complete = 90.3%

Dorsal = 9.7%

N = 705

Complete = 29.9%

Dorsal = 14.0%

Ventral = 37.9%

Edgeless = 18.2%

Perforation N = 110

Full umbo = 2.7%

Open umbo = 0.0%

Ventral = 0.0%

Dorsal = 1.8%

None = 95.5%

N = 715

Full umbo = 0.3%

Open umbo = 1.1%

Ventral = 0.1%

Dorsal = 5.4%

None = 93.0%

N = 310

Full umbo = 42.9%

Open umbo = 2.6%

Ventral = 0.0%

Dorsal = 0.3%

None = 54.2%

Height 28.2±9.5 (N = 92) 19.4±4.3 (N = 695) 33.1±8.6 (N = 242)

Length 25.4±7.3 (N = 61) 20.1±4.3 (N = 659) 33.5.±8.8 (N = 222)

Thickness 10.9±3.9 (N = 88) 8.5±2.1 (N = 685) 11.9±3.3 (N = 255)

Height (perforated) 29.6±4.6 (N = 6) 19.4±4.9 (N = 50) 36.9±6.3 (N = 89)

Maximum internal diameter of the perforation

15.3±1.2 (N = 3) 4.9±3.9 (N = 50) Stage 1: 0.9 (N = 1)

Stage 2: 4.5±2.7 (N = 30)

Stage 3: 5.6±2.9 (N = 58)

50

SI Figure 27. Glycymeris insubrica shells from Cala Arturo beach. Examples of the different weathering stages recognized, from stage 1 (at the top) through to stage 4, at the bottom.

51

G. insubrica from Cala Arturo (Calblanque, Murcia)

52

79

10

74

67

9

18

0%25

%50

%75

%10

0%

Stage 1Stage 2Stage 3Stage 4P

erfo

rate

dN

on-p

erfo

rate

d

SI Figure 28. Perforated Glycymeris shells Top. Presence of a perforation as a function of weathering stage in the G. insubrica shells from Cala Arturo. Middle. Close-up views of the perforations in two G. insubrica stage 3 shells from Cala Arturo. Bottom. Anthropically gouged and perforated G. glycymeris shell from the Early Neolithic of Gruta do Caldeirão, Portugal.

Sta

ge 1

Sta

ge 2

Sta

ge 3

Sta

ge 4

Non-perforated

7453

67 79

9

1018

0%50

%10

0%

Perforated

25%

75%

52

SI Figure 29. Cerastoderma glaucum shells from Guardamar beach. Top. Shells with predator holes. Middle.Shells with incipient dorsal perforation. Bottom. Dorsally perforated shells (note that the holes formed in areasthinned by corrosion and exfoliation).

53

SI Figure 30. Acanthocardia tuberculata shells from Guardamar beach. Top. Umbo-perforated shells; the edges of the holes are smoothed by continued abrasion of the dorsal area of the shell. Bottom. Dorsally perforated shell; the hole was formed by shock break, mimicking direct percussion, with no subsequent smoothing.

54

Supporting Information VIII: Perforated bivalves from prehistoric sites of Mediterranean Spain

In order to assess whether the characteristics of the perforated shells from Cueva de los

Aviones deviated from those found in later prehistoric times, we examined, using the same criteria and definitions applied to the modern bivalve reference collection (Supporting Information VII), the perforated Acanthocardia, Cerastoderma and Glycymeris from two major sites of Mediterranean Spain kept in the Prehistory Museum of Valencia—the Upper Paleolithic (Solutrean and Magdalenian) Cova de Parpallò (44-45) and the Early Neolithic (Cardial and Epicardial) Cova de l’Or (48). Counts and metrics are provided in SI Table 11 and SI Fig. 31, and the studied specimens are illustrated in SI Figs. 32-42.

Parpallò The Parpallò inventory (45) mentions six Cerastoderma shells, five of which are drawn; we

were able to examine these five, plus two additional specimens that we could not match to the published description. Where Acanthocardia and Glycymeris are concerned, two and five shells, respectively, had been previously reported and are the same that we examined and illustrate herewith, except for a Glycymeris of uncertain stratigraphic provenience that is not drawn and that we could not find either.

Concerning the origin of the perforations, those in the two Acanthocardia had been diagnosed as anthropic and possibly made by a drill; those in three of six Cerastoderma had been diagnosed as anthropic (one of which possibly through the use of a drill), and one as a break produced either by natural processes or by the use of direct percussion; and those in four of the five Glycymeris were also diagnosed as anthropic (one made by abrasion, another by percussion, the other two with a drill). In our examination, however, we detected tool marks in none of the shells. Moreover, their surface condition and weathering stage are consistent with a natural origin of the perforation in all cases.

The Acanthocardia (SI Fig. 32) and Cerastoderma (SI Fig. 33-34) are heavily weathered and exfoliated shells, the perforations often coincide with the most degraded area of the shell, and the edges of the perforations are smoothed and pierced by clionid holes whose distribution and placement indicate that the perforation occurred in the sea bottom, prior to beaching. The single exception is a relatively unweathered Cerastoderma that presents a large, irregular hole with sharp, fresh breaks. However, such damage, mimicking direct percussion, can occur naturally, as exemplified by the modern Acanthocardia from our reference collection illustrated in SI Fig. 30. Moreover, the fact that, in contrast with the predominance of umbo-perforated specimens in the other two taxa, Cerastoderma are principally perforated dorsally, below the umbo (six out of seven), matches the pattern seen in the modern reference collection. Where the Glycymeris are concerned (SI Fig. 35-36), the four shells that we examined all feature advanced weathering (stage 3) and, in our reference collection, 89.8% of the specimens assigned to that stage bear a natural perforation.

We conclude that all the Upper Paleolithic perforated bivalves from Parpallò that have been classified as ornamental shells correspond to naturally perforated, beach-stranded material. Deliberate collection of such material by the cave’s inhabitants is independently corroborated by three Donax trunculus shells with typical predator drill-holes (49) (SI Fig. 31).

Or The Or inventory of perforated shells (48) mentions six Acanthocardia, 11 Cerastoderma

and 33 Glycymeris and considers them all to be anthropogenic. Only four of the Acanthocardia and 16 of the Glycymeris could be made available for analysis but, as this sample corresponds to 50% of the collection, it can be consdiered as representative of the collection as a whole.

55

Like those from Parpallò, the Or Acanthocardia (SI Fig. 37) are exfoliated, decalcified and weathered specimens featuring clionid holes on the edges of perforations of smoothed appearance, all of which is consistent with natural perforation in the sea bottom, prior to beaching. The Glycymeris (SI Fig. 38-41) are all in weathering stages 2 or 3 and, in our reference collection, 43.7% of the stage 2 shells and 89.8% of the stage 3 ones bear a natural perforation. Moreover, no tool-marks were apparent on any of these shells. As in Parpallò, the Cova de l’Or shell ornaments correspond to naturally perforated, beach-collected material.

In three Glycymeris shells (F2/c5 and the two labelled H/c7; SI Figs. 38, 41), the umbo area is abrasion-flattened, as can also be seen in H1/c6, a non-perforated specimen (SI Fig. 42). In all four, however, the edges of the flattened surface are round and smooth, not at an angle with the rest of the shell, as one would expect if they were anthropogenic. Moreover, the flat areas remaining around the perforations show the same kind of pitting from bioerosion and corrosion apparent throughout the shells’ surfaces. Both the abrasion-flattening and the perforations are entirely natural processes (42), and any human involvment in the production of the shells’ extant morphologies can only have consisted of the modification of a pre-existing condition.

Conclusions A significant difference between the two sites is that larger shells were being targeted in the

Early Neolithic—the height of the Or material is 44.0±10.5 mm, as opposed to 19.4±4.3 mm at Parpallò. However, it should be noted that the latter are very small by comparison with the umbo-perforated shells of the reference assemblage, whose height is 36.9±6.3 mm (SI Tables 10-11, SI Fig. 31) (all values in the preceding are average±standard deviation). Another, possibly preservation-related difference is that ochre residues are conspicuous in eight (one Acanthocardia and seven Glycymeris) of the 20 perforated Or shells that we could examine. At this site, and in the Early Neolithic in general, the symbolic value of Glycymeris shells is further attested by their use as raw-material for the manufacture of tear-shaped beads, one of the period’s most common ornament types (and represented at Cova de l’Or by 36 specimens) (48). At Gruta do Caldeirão (Portugal), such tear-shaped beads were found in burials together with perforated whole valves (47). This Neolithic context of mass production of artificially cut, shaped and pierced Glycymeris beads makes it all the more remarkable that the perforations in all the umbo-perforated complete valves from Cova de l’Or included in our study are natural rather than anthropic.

At Parpallò, despite the smaller size of the shells, the maximum diameters of the holes are in the same range (~5 mm) seen at Cova de l’Or, and, when the totality of the archeological material that we examined is compared with the modern reference sample, it is apparent that the primary target of the prehistoric collectors consisted of shells that, irrespective of overall size, had umbo perforations in the 4.5-6.5 mm range (SI Fig. 31). In the past as much in the present, it is clear, assuming an ornamental function for the shells, that, at the time of collection, people would have used a categorical classification of the perforations (and calipers did not exist in prehistoric times anyway): “good to pass a string through” versus “not so good to pass a string through.” Bearing this in mind, the selection pattern is also shown by the p-values obtained when chi-square testing the difference in composition of the two samples (archeological versus natural) when thusly (“good” versus “not so good”) divided up: depending on the proxy used for “good” perforation sizes, 0.0245 (using the inter-quartile range of the perforations in the archeological specimens), or 0.0377 (using the modal class of the histogram of archeological perforations), both statistically significant.

This feature—possession of a hole of the appropriate size—seems therefore to have been the main criterion underlying selection, implying that color, shine and overall surface appearance were less important than threading constraints. Such a selection pattern would explain why the archeological Glycymeris are entirely made up of material in weathering stages 2 or 3, despite shells in stage 1 preserving more of the original color and being rather easy to find too, since

56

they can be found in significant numbers in the same beach thanatocenoses as the more weathered material. In our reference collection, stage 1 shells are 17.5% of the total, but only one is perforated, and with a very small, <1 mm wide hole, while 92.1% of the perforated material assigned to stages 2 or 3 features holes in the size range (0.6-9.5 mm) observed in the three archeological collections (Aviones, Parpallò and Cova de l’Or). These inferences are consistent with the fact that archeological Glycymeris often present residues of ochre whose overall distribution on the shells indicates they once were entirely painted—something one would not expect if freshness and original color impacted the meaning attached to the shell in any significant way.

Although not considered in this discussion because of uncertainty regarding their representativity, we also examined perforated Acanthocardia (two shells) and Glycymeris (13 shells) from the Early Neolithic cave site of La Sarsa (Valencia) (48) and the Eneolithic open air settlement of Las Amoladeras (Murcia) (50). These samples match point by point the characteristics of those presented above, as do, based on the published descriptions, the perforated Glycymeris from the Upper Paleolithic of Cova Beneito (49) and the perforated Acanthocardia, Cerastoderma and Glycymeris shell ornaments from the Upper Paleolithic and Mesolithic of Cantabria and the Ebro valley (46).

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SI Table 11. Size and weathering of perforated bivalve shells from the Solutrean and Magdalenian of Cova de Parpallò and the Early Neolithic of Cova de l’Or (Valencia, Spain) (all measurements are in mm and given as average±standard deviation). Attributes Parpallò Or

Acanthocardia 2 4

Exfoliated 2 4

With sponge holes 2 4

Umbo-perforated 1 3

Dorsal-perforated 1 1

Ochred — 1

Height 41.2±8.6 34.4±6.8

Length 38.9±6.6 34.1±5.7

Perforation size (maximum internal diameter) 5.7±0.9 3.4±0.9

Cerastoderma 7 —

Exfoliated 6 —

With sponge holes 6 —

Umbo-perforated 1 —

Dorsal-perforated 6 —

Ochred — —

Height 24.9±2.7 —

Length 26.5±2.9 —

Perforation size (maximum internal diameter) 3.0±0.8 —

Glycymeris 4 16

Weathering stages 2-3 4 16

With sponge holes 4 15

Umbo-perforated 4 16

Dorsal-perforated — —

Ochred — 7

Height 19.4±4.3 44.0±10.5

Length 20.2±3.3 46.6±10.7

Perforation size (maximum internal diameter) 4.6±2.7 4.6±1.5

58

SI Figure 31. Top. Donax trunculus from Parpallò bearing typical predator drill-holes. Middle. Relative frequency histograms of umbo perforation sizes in the archeological and the reference collections. Bottom. Scatter plot of height versus umbo perforation size in the archeological and the reference collections.

1

2

3

1. Lower Magdalenian (Centro Oeste, 1.5-1.7 m); 2-3. Basal Upper Magdalenian (1.2-1.5 m and Talud capa 5)

maximum internal diameter of perforation (mm)

0

10

20

30

40

50

0.5-

2.5

2.5-

4.5

4.5-

6.5

6.5-

8.5

8.5-

10.5

10.5

-12.

5

>12.

5 mm

%

Modern[N=89]

0

10

20

30

40

50

0.5-

2.5

2.5-

4.5

4.5-

6.5

6.5-

8.5

8.5-

10.5

10.5

-12.

5

>12.

5

%

mm

Aviones,Or and Parpallò[N=21]

shell height (mm)

maximum internal diameter of perforation (mm)

0

5

10

15

20

15 20 25 30 35 40 45 50 55 60 65

Stage 1, modern

Stage 2, modern

AvionesOr

Parpallò

Stage 3, modern

59

Sector O(1.2-1.5 m),Lower Magdalenian;height - 35.1 mm

Sector L (5.5-5.75 m), Middle Solutrean; height - 47.2 mm

SI Figure 32. Cova de Parpallò. Upper Paleolithic perforated shells of Acanthocardia tuberculata. Note the exfoliation and the sponge holes associated with the perforations.

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SI Figure 33. Cova de Parpallò. Upper Paleolithic perforated shells of Cerastoderma sp. Note the exfoliation and the sponge holes associated with the perforations.

Centro Oeste, Capa 3,Upper Magdalenian; height - 27.2 mm

P-6332, unknown level; height - 27.3 mm

P-6325 (Sector P, 5.75-6 m), Middle Solutrean; height - 28.0 mm

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SI Figure 34. Cova de Parpallò. Upper Paleolithic perforated shells of Cerastoderma sp. Note the exfoliation and the sponge holes associated with the perforations in three of the shells. P-6350 is the only fresh, relatively unweathered specimen in the assemblage; it bears a shock perforation that mimicks direct percussion but is known to occur in natural thanatocenoses (cf. SI Fig. 30).

Talud(3-3.5 m),Lower Magdalenian;height - 23.3 mm

P-6350 (Galeria Este, capa 6), Solutrean or Magdalenian; height - 23.7 mm

P-6319 (Sector P, 3.5-3.75 m), Lower Magdalenian; height - 20.5 mm

P-6327 (Sector C, 1.7-2 m), Upper Magdalenian; height - 24.1 mm

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SI Figure 35. Cova de Parpallò. Upper Paleolithic umbo-perforated valves of Glycymeris insubrica (both weathering stage 3; note the decalcification of the smaller shell).

Centro OesteCapa 3, Upper Magdalenian; height - 15.8 mm

Sector P2-2.2 m,Upper Magdalenian;height - 20.5 mm

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SI Figure 36. Cueva de Parpallò. Upper Paleolithic umbo-perforated valves of Glycymeris insubrica (both weathering stage 3).

P-6330 (0.2-0.4 m), Upper Magdalenian;height - 25.1 mm

Sector L (4.5-5.25 m), Upper Solutrean; height - 16.3 mm

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SI Figure 37. Cova de l’Or (Early Neolithic). Dorsal- (topmost) and umbo-perforated valves of Acanthocardia tuberculata. Note the significant weathering, including exfoliation and sponge holes.

H2/c6 – height: 29.4 mm

H1/c7 – height: 43.0 mm

H1/c7 – height: 28.4 mm

H4/c7 – height: 36.8 mm

65

SI Figure 38. Cova de l’Or (Early Neolithic). Umbo-perforated valves of Glycymeris insubrica (weathering stages 2 and 3).

H/c7 – height: 34.4 mm

H/c7 – height: 41.2 mm

H4/c6 – height: 28.7 mm

H4/c6 – height: 52.2 mm

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SI Figure 39. Cova de l’Or (Early Neolithic). Umbo-perforated valves of Glycymeris insubrica (weathering stages 2 and 3).

H4/c5 – height: 33.5 mm

H3/c6 – height: 45.4 mm

H2/c6 – maximum internal diameter of the perforation: 2.2 mm

H3/c6 – height: 51.6 mm

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H2/c6 – height: 45.7 mm

H2/c3 – height: 49.8 mm

H2/c2 – height: 55.1 mm

H1/c7 – height: 52.0 mm

SI Figure 40. Cova de l’Or (Early Neolithic). Umbo-perforated valves of Glycymeris insubrica (weathering stage 2).

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SI Figure 41. Cova de l’Or (Early Neolithic). Umbo-perforated valves of Glycymeris insubrica (weathering stages 2 and 3).

H1/c4 – height: 44.8 mm

Grieta Norte/c13 – height: 40.8 mm

F2/c5 – height: 23.2 mm

H1/c6 – height: 61.1 mm

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SI Figure 42. Cova de l’Or Glycymeris. Close-up views of the abrasion-flattened, perforated umbos of the two H/c7 shells in SI Figure 38 (top and middle) and a non-perforated shell (H1/c6) with a similar weathering pattern (bottom). The smooth edges of the flattened areas and the pitting from bioerosion and corrosion—identical to that seen elsewhere in the shells—show that these features, including the perforations, are natural. Although the vertical striations apparent in the middle image could be anthropogenic in part, they can represent no more than modification of a pre-existing natural perforation.

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