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Proceedings of the National Academy of Sciences of the United States of America logoLink to Proceedings of the National Academy of Sciences of the United States of America
. 2017 Oct 23;114(45):11856–11860. doi: 10.1073/pnas.1707450114

Competing English, Spanish, and French alabaster trade in Europe over five centuries as evidenced by isotope fingerprinting

W Kloppmann a,1, L Leroux b, P Bromblet c, P-Y Le Pogam d, A H Cooper e, N Worley f, C Guerrot a, A T Montech a, A M Gallas a, R Aillaud g
PMCID: PMC5692548  PMID: 29078309

Significance

Gypsum alabaster in medieval artwork equaled or even surpassed the importance of marble for religious sculptures and effigies. Based on isotope fingerprints, a large corpus of European alabaster sculptures are linked to historical quarries and trade in the Middle Ages and Renaissance period. We demonstrate that English alabaster export was competed on the continent by the Spanish and by a particularly long-lived (>500 y) French Alpine trade. Our study reveals historical trade routes and transport, the diversity of supply of medieval artists and workshops, as well as the presence and provenance of restoration materials.

Keywords: alabaster, provenance, isotope fingerprinting, Middle Ages, Renaissance

Abstract

A lack of written sources is a serious obstacle in the reconstruction of the medieval trade of art and art materials, and in the identification of artists, workshop locations, and trade routes. We use the isotopes of sulfur, oxygen, and strontium (S, O, Sr) present in gypsum alabaster to unambiguously link ancient European source quarries and areas to alabaster artworks produced over five centuries (12th–17th) held by the Louvre museum in Paris and other European and American collections. Three principal alabaster production areas are identified, in central England, northern Spain, and a major, long-lived but little-documented alabaster trade radiating from the French Alps. The related trade routes are mostly fluvial, although terrestrial transport crossing the major river basin borders is also confirmed by historical sources. Our study also identifies recent artwork restoration using Italian alabaster and provides a robust geochemical framework for provenancing, including recognition of restoration and forgeries.

Alabaster was one of the preferred materials of medieval and Renaissance sculptors due to its ease of carving in elaborate detail and its translucent whiteness; it is much more than a mere substitute “if marble will not serve” (1). Alabaster was indeed chosen for many royal (2) and papal (3) effigies, for innumerable religious artworks, and for monuments.

However, the homogeneous nature and similar characteristics of alabaster from different areas make it impossible to determine its provenance on the basis of mineralogy, chemistry, and texture alone (4–6). Historically, varieties of both calcite and gypsum/anhydrite were termed “alabaster.” The first, known as “Egyptian” or “oriental” alabaster (7), quarried at the Egyptian town of Alabastron, gave its name to both materials. Even if stringent chemical distinction only became possible in the 18th century (8), sulfate and calcite alabaster were already used and distinguished in antique times (e.g., in Theophrastus’ treaty on stones, ref. 9). Here we focus on the “true” alabaster, the noble variety of gypsum (CaSO4·2H2O) or anhydrite (CaSO4), widely used in medieval Europe.

The most abundant historical evidence of the European alabaster trade comes from the Midlands of England, mainly in the Dove and Trent valleys to the west of Nottingham. These deposits were considered to be the most productive and widely used European source. Alabaster from the English Midlands was worked by the “alabastermen” from the 12th century (2, 10) until 1550, when an Act of Parliament triggered the iconoclastic crisis of the Reformation, stopping all production of religious sculpture. From this time on, only funeral effigies were permitted and these continued to be produced in great number (10, 11). Early English alabaster export is documented both for artwork, e.g., to Rome (1382), Seville (1390), and Nantes (1408) (10), and for sculptural raw materials, e.g., to Fécamp Abbey in Normandy in 1414 (10, 12). After the banning of religious representations, shiploads of alabaster artworks were sent to France (13). In England, only a few sculptures escaped the plaster furnaces by being hidden and were retrieved centuries later (14). In contrast, western and northern France was inundated with outlawed English artworks.

Another well-known center of the alabaster trade was northern Spain. Spanish alabaster from the medieval quarries at Beuda, Sarral, and the Ebro Valley was the material of choice for sculptors working for the Crown of Aragon from the 14th to 16th centuries, as evidenced by the particularly large altarpieces in Aragon and Catalonia. Trade from this area spread north of the Pyrenees (15), into Portugal, and as far as the Kingdom of Naples (16).

Little is known about the distribution from other historical alabaster deposits in continental Europe. Whereas the various sources of classical marble have been studied for many decades (17, 18), the scarce documentary evidence on alabaster could not be verified by any independent geochemical method, a situation that Cheetham in his landmark monograph (10) considered as “most frustrating.”

Our pilot study (19) tested isotope fingerprints (Sr, S, O) as an independent method to link artworks to their source areas, and developed an associated analytical protocol: Tiny flakes (<20 mg) of alabaster are dissolved in distilled water at 50 °C, and the dissolved sulfate is precipitated as BaSO4 for S- and O-isotope analysis by continuous flow isotope ratio mass spectrometer (CF-IRMS). Aliquots of the solutions are purified by ion exchange for Sr-isotope analysis by thermal ionization mass spectrometer (TIMS). Full details of the methods are provided in SI Materials and Methods. The sparse initial database of European historical quarries has now been greatly enlarged and includes virtually all of the known pre-19th century sites in France, plus major deposits in England, Spain, Germany, and Italy (Fig. 1 and Table S1). Strong interdeposit contrast and good intradeposit homogeneity of the isotope fingerprints (Fig. 2 and Table S2) were demonstrated, particularly when strontium and sulfur are combined. Oxygen isotopes are slightly more scattered, but are essentially consistent (albeit with some overlap) with the Sr and S data. In addition, some sources are strongly depleted or enriched in 18O, strengthening the method’s discriminating power (Fig. S1).

Fig. 1.

Fig. 1.

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Original location of analyzed artworks, attributed provenance, and schematic links to historical quarries.

Table S1.

European alabaster deposits and their isotopic composition

δ34S ± 0.3 (1σ) δ18O ± 0.5 (1σ)
Country Region Location Quarry/Situation X Y Geological age ‰ vs. CDT ‰ vs. SMOW 87Sr/86Sr 2σ, m 87Sr/86Sr
England Cumbria Vale of Eden, Cumbria “Houtsay” quarry, Newbiggin Mine 54° 38′ 34.1″ N −2° 35′ 1.6″ W Permian, Wulchiapingian (Eden Shales Fm., B-Bed) 11.8 10.2 0.707647 0.000007
England North Yorkshire Ripon Parks, Borough of Harrogate, North Yorkshire Outcrop 54° 10′ 17.5″ N −1° 31′ 47.2″ W Permian, Wulchiapingian (Zechstein Gp, Edlington Fm.) 11.4 9.4 0.707218 0.000010
England North Yorkshire Ripon Parks, Borough of Harrogate, North Yorkshire Outcrop 54° 10′ 17.5″ N −1° 31′ 47.2″ W Permian, Wulchiapingian (Zechstein Gp, Edlington Fm.) 11.0 9.8 0.707087 0.000007
England East Midlands Newark Nottinghamshire “Kilvington” quarry 52° 58′ 51.65″ N −0° 48′ 44.12″ W Triassic, Norian (Mercia Mudst. Gp.) 14.0* 14.1 0.709058 0.000007
England East Midlands Chellaston, Derbyshire Outcrop close to the Medieval quarry 52° 52′ 21.3921.39 −1° 25′ 36.0336.03 Triassic, Norian (Mercia Mudst. Gp) 13.7* 14.2 0.709209 0.000009
England East Midlands Fauld Mine, Staffordshire Fauld Mine 52° 50′ 37.85″ N −1° 44′ 16.94″ W Triassic, Norian (Mercia Mudst. Gp.) 13.3* 11.7 0.709182 0.000007
England East Midlands Fauld Mine, Staffordshire Fauld Mine 52° 50′ 37.85″ N −1° 44′ 16.94″ W Triassic, Norian (Mercia Mudst. Gp.) 13.2* 11.1 0.709134 0.000007
England East Midlands Fauld Mine, Staffordshire Fauld Mine 52° 50′ 37.85″ N −1° 44′ 16.94″ W Triassic, Norian (Mercia Mudst. Gp.) 13.6* 11.8 0.709170 0.000006
England East Midlands Fauld Mine, Staffordshire Fauld Mine 52° 50′ 37.85″ N −1° 44′ 16.94″ W Triassic, Norian (Mercia Mudst. Gp.) 13.2 12.4 0.709204 0.000007
England East Midlands Fauld Mine, Staffordshire Fauld Mine 52° 50′ 37.85″ N −1° 44′ 16.94″ W Triassic, Norian (Mercia Mudst. Gp.) 13.6 13.0 0.709173 0.000009
England East Midlands Fauld Mine, Staffordshire Fauld Mine 52° 50′ 37.85″ N −1° 44′ 16.94″ W Triassic, Norian (Mercia Mudst. Gp.) 13.6 13.1 0.709267 0.000006
France Alps, Isère Notre-Dame-de-Mésage Quarries “Saint-Firmin” 45° 4′ 8.88″ N 5° 45′ 33.41″ E Triassic (Keuper) 16.0* 12.7 0.707835 0.000009
France Alps, Isère Notre-Dame-de-Mésage Quarries “Saint-Firmin” 45° 4′ 11.7″ N 5° 45′ 33.6″ E Triassic (Keuper) 15.7 14.0 0.707837 0.000006
France Alps, Isère Notre-Dame-de-Mésage Quarries “Saint-Firmin” 45° 4′ 11.7″ N 5° 45′ 33.6″ E Triassic (Keuper) 15.2 11.9 0.707820 0.000006
France Alps, Isère Notre-Dame-de-Mésage Quarries “Saint-Firmin” 45° 4′ 19.9″ N 5° 45′ 36.02″ E Triassic (Keuper) 15.56 12.9 0.707858 0.000006
France Alps, Isère Notre-Dame-de-Mésage Quarry “Plan d’Agneau”, Vizille 45° 5′ 22.26″ N 5° 46′ 30.31″ E Triassic (Keuper) 16.2 13.5 0.707780 0.000009
France Alps, Isère Notre-Dame-de-Mésage Quarry Champs-sur-Drac 45° 4′ 37.7″ N 5° 44′ 32,83″ E Triassic (Keuper) 15.5 12.0 0.707915 0.000006
France Alps, Isère Notre-Dame-de-Mésage Quarry Saint-Pierre-de-Mésage 45° 2′ 58.18″ N 5° 45′ 41.45 E Triassic (Keuper) 15.5 15.0 0.708018 0.000005
France Alps, Isère Notre-Dame-de-Mésage Quarry Saint-Pierre-de-Mésage 45° 2′ 58.18″ N 5° 45′ 41.45 E Triassic (Keuper) 15.6 12.4 0.707848 0.000007
France Alps, Savoie Saint-Jean-de-Maurienne, Savoie Quarry “Les Rossières” 45° 15′ 35″ N 6° 19′ 15″ E Triassic 16.1* 11.7 0.707682 0.000008
France Alps, Savoie Saint-Jean-de-Maurienne, Savoie Quarry “Les Rossières” 45° 15′ 35″ N 6° 19′ 15″ E Triassic 16.3* 11.2 0.707655 0.000010
France Aquitaine Moulidars, Charente Quarry 45° 39′ 43.49″ N 0° 2′ 32.49″ W Jurassic, Tithonian to Berriasian 18.7 17.6 0.707182 0.000010
France Burgundy Mâlain, Côte d’Or Quarry 47° 20′ 00″ N 4° 47′ 25″ E Triassic, Carnian or Norian 15.9* 13.7 0.709614 0.000008
France Burgundy Berzé-la-Ville, Saône -et-Loire Quarry/gypsum oven 46° 21′ 52.98″ N 4° 42′ 24.46″ E Triassic 14.8 11.0 0.709188 0.000007
France Jura Salins-les-Bains, Jura Quarry in the town center 46° 57′ 00″ N 5° 52′ 45″ E Triassic (upper Keuper) 16.3* 13.1 0.708099 0.000010
France Jura Salins-les-Bains, Jura Quarry in the town center 46° 57′ 00″ N 5° 52′ 45″ E Triassic (upper Keuper) 16.4* 14.0 0.708104 0.000008
France Jura Salins-les-Bains, Jura Quarry “Le Boisset” 46° 54′ 35″ N 5° 53′ 48″ E Triassic (upper Keuper) 16.4* 14.2 0.708030 0.000008
France Lorraine Klang, Moselle Quarry 49° 19′ 15″ N 6° 21′ 40″ E Triassic, (upper Keuper) 10.4* 15.7 0.708418 0.000008
France Paris region Thorigny-sur-Marne, Seine-et-Marne Quarry “Vallières” 48° 54′ 3.65″ N 2° 43′ 18.42″ E Cenozoic, Bartonian (Ludian) 21 13.1 0.707788 0.000007
France Paris region Annet sur Marne, Seine-et-Marne “Carrefour de la Violette” quarry 48° 55′ 25″ 2° 43′ 37″ Cenozoic, Bartonian (Ludian) 17 18.6 0.707890 0.000006
France Provence Boscodon, Hautes-Alpes Historical exploitation, Bragousse torrent 44° 28′ 56.47″ N 6° 27′ 15.09″ E Triassic (Keuper) 15.8 12.9 0.707676 0.000008
France Provence Saint-Geniez, Alpes de Haute Provence Quarry 44° 14′ 45.35″ N 6° 4′ 12.73″ E Triassic (Keuper) 15.3 12.2 0.708046 0.000007
France Provence Lazer, Hautes-Alpes Quarry 44° 20′ 30.5″ N 5° 50′ 36.4″ E Triassic (Keuper) 16.6 12.4 0.707704 0.000007
France Provence Malaucène, Vaucluse “Les Gippières” quarry 44° 10′ 13″ N 5° 9′ 4″ E Cenozoic, Oligocene 18.6 18.8 0.707587 0.000007
France Provence Malaucène, Vaucluse “Les Gippières” quarry 44° 10′ 13″ N 5° 9′ 4″ E Cenozoic, Oligocene 18.4 18.5 0.707594 0.000006
France Provence Malaucène, Vaucluse “Les Gippières” quarry 44° 10′ 13″ N 5° 9′ 4″ E Cenozoic, Oligocene 17.9 19.5 0.707603 0.000006
France Provence Malaucène, Vaucluse “Les Gippières” quarry 44° 10′ 13″ N 5° 9′ 4″ E Cenozoic, Oligocene 18.7 18.6 0.707590 0.000007
Germany Harz Nordhausen, Harz “Winkelberg” quarry, gypsified Sangershausen anhydrite 51° 31′ 54.44″ N 10° 49′ 10.94″ E Permian, Wuchiapingian (Zechstein 2, Strassfurt episode) 11.6 9.8 0.707225 0.000007
Germany Harz Nordhausen, Harz “Winkelberg” quarry, gypsified Sangershausen anhydrite 51° 31′ 54.44″ N 10° 49′ 10.94″ E Permian, Wuchiapingian (Zechstein 2, Strassfurt episode) 11.7 10.5 0.707178 0.000007
Germany Harz Nordhausen, Harz “Kahleberg” quarry, gypsified Werra anhydrite 51° 32′ 8.48″ N 10° 48′ 29.48″ E Permian, Wuchiapingian (Zechstein 1, Werra episode) 11.4 9.9 0.707024 0.000007
Germany Harz Nordhausen, Harz “Kahleberg” quarry, gypsified Werra anhydrite 51° 32′ 8.48″ N 10° 48′ 29.48″ E Permian, Wuchiapingian (Zechstein 1, Werra episode) 11.5 9.6 0.707007 0.000008
Spain Aragon Quinto de Ebro, Aragon “Aragonesa de l’Albastro” quarry 41° 25′ 47.95″ N 0° 30′ 50.67″ W Cenozoic, Miocene 14.5* 14.5 0.707939 0.000008
Spain Aragon Fuentes de Ebro, Aragon Quarry, road to Roden 41° 30′ 14.91″ N 0° 37′ 49.71″ W Cenozoic, Miocene 11.1* 16.0 ± 0.6 0.708510 0.000008
Spain Catalonia Sarral, Catalonia Quarries south of the village 41° 26′ 31.64″ N 1° 13′ 15.56″ E Cenozoic, Eocene 16.5* 14.7 0.707886 0.000008
Spain Catalonia Beuda, Catalonia Quarry 42° 14′ 12.01″ N 2° 44′ 02.35″ E Cenozoic, Eocene 19.8* 11.3 0.707794 0.000008
Spain Catalonia Beuda, Catalonia Quarry 42° 14′ 12.01″ N 2° 44′ 02.35″ E Cenozoic, Eocene 20.2* 11.8 0.707781 0.000008
Spain Catalonia Beuda, Catalonia Quarry 42° 14′ 12.01″ N 2° 44′ 02.35″ E Cenozoic, Eocene 19.8* 11.6 0.707769 0.000009
Italy Tuscany Volterra, Tuscany Quarry between Mazzolla and Spicchiaiolona 43° 22′ 41″ 10° 55′ 35″ Cenozoic, Miocene, Messinian 23.6 14.2 0.708893 0.000009
Italy Tuscany Volterra, Tuscany Quarry between Mazzolla and Spicchiaiolona 43° 22′ 41″ 10° 55′ 35″ Cenozoic, Miocene, Messinian 26.3 15.5 ± 0.6 0.708771 0.000008
Italy Tuscany Volterra, Tuscany Underground mine between Mazzolla and Spicchiaiolona 43° 22′ 41″ 10° 55′ 35″ Cenozoic, Miocene, Messinian 20.2 15.2 0.708635 0.000008
Italy Tuscany Volterra, Tuscany Castellina Marittima KNAUF quarry 43° 25′ 24″ 10° 33′ 20″ Cenozoic, Miocene, Messinian 22.8 14.8 0.708661 0.000008
Italy Tuscany Volterra, Tuscany Castellina Marittima KNAUF quarry 43° 25′ 24″ 10° 33′ 20″ Cenozoic, Miocene, Messinian 23 14.0 0.708801 0.000008
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*

S, O, and Sr data reported in ref. 19, external errors for δ34S (1σ) = 0.4‰.

Fig. 2.

Fig. 2.

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δ34S versus 87Sr/86Sr ratios of historical alabaster quarries in France, England, Spain, Italy, and Germany, including data from ref. 19. The data fields are delimited by 2σ confidence ellipses (95% confidence level).

Table S2.

Isotope data of the studied artwork regrouped by provenance

δ34S ± 0.3 (1σ) δ18O ± 0.5 (1σ)
Artwork Century ‰ vs. CDT ‰ vs. SMOW 87Sr/86Sr 2σ(m) 87Sr/86Sr
England, East Midland Basin, Nottingham region
 Statue: The kiss of Judas 14 13.4 13.4 0.709194 0.000009
 Altarpiece: Castelnau-Bretenoux 14 13.4 n.d. 0.709231 0.000009
 Saint Michael overwhelming the demon 15 13.5 13.7 0.709140 0.000008
 Allegory of the consistency in adversity 16 13.7 13.3 0.709215 0.000008
 Bas-relief: Christ in the Garden of Gethsemane, Saint Paul, Melchisédech 16 13.4 13.8 0.709149 0.000009
 Statue: Saint Jérôme 16 13.5 12.9 0.709194 0.000007
 Statue: Head of the Christ 16 13.8 13.4 0.709130 0.000007
 Group: Saint Anne educating the Virgin Mary 16 13.2 14.1 0.709165 0.000006
 Altarpiece, Calais, église Notre-Dame 17 13.6 12.8 0.709181 0.000007
 Altarpiece, Calais, église Notre-Dame 17 13.3 12.5 0.709167 0.000007
 Altarpiece, Calais, église Notre-Dame 17 13.8 12.3 0.709195 0.000007
 Statue: Seated greyhound 17 13.2 11.5 0.709070 0.000008
France, Isère, Notre-Dame-de-Mésage
 Capital 12 15.5 13.5 0.707827 0.000006
 Fragment no. 195 'Tomb of Saint Lazare 12 15.5 12.9 0.708024 0.000008
 Statue: Resurrection of a young girl of Isle-sur-Sorgue 14 15.2 13.1 0.707786 0.000007
 Carrying of the Cross 14 15.1 12.3 0.707795 0.000007
 Recumbent effigy: Pope Innocent VI 14 15.4 13.1 0.707793 0.000008
 Bas-relief: Massacre of the Innocents 14 15.3 11.8 0.707800 0.000006
 Recumbent effigy: Cardinal Guillaume II d’Aigrefeuille, head 14 15.3 11.5 0.707794 0.000008
 Recumbent effigy: Cardinal Guillaume II d’Aigrefeuille, apostle with book 14 15.7 12.1 0.707804 0.000008
 Tomb: Pope Jean XXII, deacon holding a book 14 15.6 ± 0.4 12.9 0.707790 0.000008
 Tomb: Pope Innocent VI, angel with thurible 14 15.3 12.2 0.707793 0.000007
 Tomb: Cardinal Philippe Cabassole, Saint Jacques 14 15.4 11.9 0.707800 0.000007
 Mourner keeping a book, tomb of Jean de France, the Duke of Berry 15 15.4 12.6 0.707871 0.000008
 Statue: Head of a bearded man 15 15.7 14.9 0.708087 0.000007
 Statue: Saint Antoine, Arvillard 15 15.6 14.1 0.707935 0.000006
 Recumbent effigy: Cardinal Jean de Lagrange 15 15.6 12 0.707793 0.000008
 Tomb: Cardinal Jean de Lagrange, ange de l’Annonciation 15 15.5 11.7 0.707789 0.000008
 Tomb: Cardinal Jean de Lagrange, apostle presenting Louis d’Orléans 15 15.6 11.4 0.707805 0.000009
 Tomb: Cardinal Jean de Lagrange, fragment of a head 15 15.6 11.3 0.707797 0.000007
 Tomb: Cardinal Martin de Salva, Saint Paul 15 15.4 11.6 0.707801 0.000006
 Recumbent effigy: Jeanne de Penthièvre 16 15.1 13.9 0.707798 0.000006
 Recumbent effigy: Renée d’Orléans 16 15.1 13.1 0.707791 0.000007
 Statue: Virgin with child 16 15.2 12.6 0.707782 0.000007
 Statue: Tomb of Amiral Chabot: genius, right hand 16 15.2 13.8 0.707814 0.000009
 Statue of Saint Stephen: Altarpiece of Tristan de Salazar, 16 15.5 12.7 0.707790 0.000006
 Bas-relief: Dormition of the Virgin 16 15.6 13.6 0.707792 0.000007
 Tomb: Jean III d’Humières 16 15.6 13.9 0.707793 0.000006
 Virgin with the Child 16 15.4 13 0.707783 0.000007
 Statue: Virgin Mary 16 15.5 13.4 0.707790 0.000006
 Statue: Angel as musician with organ 16 15.5 14.6 0.707774 0.000007
 Group: Saint Anne educating the Virgin Mary 16 15.6 15.7 0.708036 0.000006
 Tomb: Mausoleum of François de Bonne, Constable of Lesdiguières 17 15.7 12.4 0.707787 0.000007
 Statue: St John Baptist 14 15.4 11.7 0.707799 0.000007
France, Savoie, Saint-Jean-de-Maurienne
 Recumbent effigy: Monsignor Ogier Morizet 15 15.8 11.0 0.707656 0.000007
 Statue: Virgin with child 16 15.9 13.1 0.707675 0.000008
France, Burgundy, Berzé-la-Ville
 Sculpted facade of the Jacques d’Amboise palace, drill core 3 15 15.1 12 0.709161 0.000007
France, Provence, Malaucène
 Recumbent effigy: Pope Urbain V 14 18.5 18.3 0.707583 0.000007
 Recumbent effigy: Pope Urbain V 14 18.3 19 0.707597 0.000008
 Statue: Angel of the Annunciation 14 18.3 19.3 0.707599 0.000007
 Statue: Virgin of the Annunciation 14 18.2 18.5 0.707600 0.000007
Italy, Tuscany, Volterra region
 Statue: Virgin of the Annunciation rest 22.6 15.1 0.708896 0.000008
Nonidentified
 Bas-relief: Tomb of Claude de Guise (black alabaster) 16 14.2 11.6 0.708520 0.000007
 Bas-relief: Tomb of Claude de Guise (white alabaster) 16 15.5 14.4 0.708211 0.000009
 Statue: Saint holding an open book 16 15.6 14.8 0.708186 0.000008
 Bas-relief: Entombment of Christ 16 15.6 14.9 0.708124 0.000006
 Sculpted facade of the Jacques d’Amboise palace, drill core 2 rest 15.6 13 0.708085 0.000009
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Fig. S1.

Fig. S1.

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34S versus δ18O of historical alabaster quarries in France, England, Spain, Italy, and Germany, including data from ref. 19. The data fields are delimited by 2σ confidence ellipses (95% confidence level).

A large corpus of major alabaster artworks [66 samples including 9 already characterized (19)] has been analyzed (Tables S2 and S3). The Louvre Museum in Paris provided 19 samples from 14th–17th century sculptures. The Petit-Palais Museum in Avignon and the collection of the Chartreuse in Villeneuve-lez-Avignon added 13 samples from 12 effigies, along with altarpieces from the funeral monuments of popes and cardinals of French papacy of the second half of the 14th century and during the Great Schism (1378–1417). Other individual pieces were made available from American (Cleveland Museum of Art, Chicago Art Institute), Swedish, English, and French collections, galleries, and churches.

Table S3.

Artwork: Date of creation, original and current situation, and provenance of the material used, including artwork reported in ref. 19

Artwork Century/Period Original monument/situation Current situation Provenance
Statue: The kiss of Judas 14 14th cent. (1320–1340) ? Paris, Cluny Museum - Invent.Cl. 23419 English Midlands, Dove and Trent valleys
Altarpiece: Castelnau-Bretenoux 14 14th cent. ? Castelnau-Bretenoux Castle, Invent. 359, panel 4 English Midlands, Dove and Trent valleys
Saint Michael overwhelming the demon 15 Second quarter 15th cent. Souvigné (Indre-et-Loire, France) Paris, Louvre Museum, Sculptures Department (France) - Invent. RF 3465 English Midlands, Dove and Trent valleys
Oudart de Bournonville tomb (statue of a Lion)* 16 Around 1585 Hénin-Beaumont, church Saint-Martin (Pas-de-Calais, France) Arras, Museum of Fine Arts (Pas-de-Calais, France) English Midlands, Dove and Trent valleys
Oudart de Bournonville tomb (fragment)* 16 Around 1585 Hénin-Beaumont, church Saint-Martin (Pas-de-Calais, France) Arras, Museum of Fine Arts (Pas-de-Calais, France) English Midlands, Dove
Gustav Vasa monument, fragments of broken obelisk* 16 Around 1570 Uppsala Cathedral (Sweden) Uppsala Cathedral (Sweden) English Midlands, Dove and Trent valleys
Allegory of the consistency in adversity 16 Middle 16th cent. ? Paris, Louvre Museum, Sculptures Department (France) - Invent.RF 3647 English Midlands, Dove and Trent valleys
Bas-relief: Christ in the Garden of Gethsemane, Saint Paul, Melchisédech 16 1582–1590 Paris, church Saint-Étienne-du-Mont Paris, Louvre Museum, Sculptures Department (France) - Invent. RF 4040 English Midlands, Dove and Trent valleys
Statue: Saint Jérôme 16 16th cent. Cambrai, former cathedral destroyed in 1796 (Nord, France) Paris, curch Notre-Dame de Bonne Nouvelle English Midlands, Dove and Trent valleys
Statue: Head of the Christ 16 16th cent. Cambrai (?) (Nord, France) Lille, Palais des Beaux-Arts Museum (Nord, France) English Midlands, Dove and Trent valleys
Group: Saint Anne educating the Virgin Mary 16 16th cent. Ecouen Castle (?, Val-d’Oise, France Paris, church Saint-Leu-Saint-Gilles English Midlands, Dove and Trent valleys
Altarpiece, Calais, église Notre-Dame (three samples) 17 1624–1628 Calais, church Notre-Dame (Pas-de-Calais, France) Calais, church Notre-Dame (Pas-de-Calais, France) English Midlands, Dove and Trent valleys
Statue: Seated greyhound 17 Around 1635–1640 Supposedly a decoration of a grotto of Wilton House gardens, Salisbury (Witshire, England) Daniel Katz Gallery (London, UK) English Midlands, Dove and Trent valleys
Capital 11? Romanesque period Saint-Martin-d’Uriage, chapel of Saint-Nizier-d’Uriage (Isère, France) Saint-Martin-d’Uriage, chapel of Saint-Nizier-d’Uriage (Isère, France) France, Isère, Notre-Dame-de-Mésage
Fragment no. 195 ‘Tomb of Saint Lazare 12 1170–1189 Autun, Cathedral Saint-Lazare (Saône-et-Loire, France) Autun, Rolin Museum (Saône-et-Loire, France) France, Isère, Notre-Dame-de-Mésage
Statue: Resurrection of a young girl of Isle-sur-Sorgue 14 Second quarter 14th cent. 1370–1373 Apt, church of the Cordeliers (Vaucluse, France) Paris, Louvre Museum, Sculptures Department (France) - Invent. RF 1676 France, Isère, Notre-Dame-de-Mésage
Carrying of the Cross 14 Second quarter 14th cent. ? Paris, Louvre Museum, Sculptures Department (France) - Invent. RF 3630 France, Isère, Notre-Dame-de-Mésage
Recumbent effigy: Pope Innocent VI 14 1361–1362 Villeneuve-les-Avignon, chartreuse Notre-Dame-du-Val-de-Bénédiction (Gard, France) Villeneuve-les-Avignon, chartreuse Notre-Dame-du-Val-de-Bénédiction (Gard, France) France, Isère, Notre-Dame-de-Mésage
Bas-relief: Massacre of the Innocents 14 Around 1331–1342 Hautecombe, chapel des princes de l’abbatiale Chambéry, Museum of Fine Arts (Savoie, France) - Invent.D8694 France, Isère, Notre-Dame-de-Mésage
Recumbent effigy: Cardinal Guillaume II d’Aigrefeuille, head 14 14th cent. Avignon, church Saint-Martial (Vaucluse, France) Avignon, Petit Palais Museum (Vaucluse, France) - Invent.N 227 A France, Isère, Notre-Dame-de-Mésage
Recumbent effigy: Cardinal Guillaume II d’Aigrefeuille, apostle with book 14 14th cent. Avignon, church Saint-Martial (Vaucluse, France) Avignon, Petit Palais Museum (Vaucluse, France) - Invent.D 96 Avignon France, Isère, Notre-Dame-de-Mésage
Tomb: Pope Jean XXII, deacon holding a book 14 After 1334 Avignon, Cathedral Notre-Dame des Doms (Vaucluse, France) Avignon, Petit Palais Museum (Vaucluse, France) - Invent.N 55 A France, Isère, Notre-Dame-de-Mésage
Tomb: Pope Innocent VI, angel with thurible 14 14th cent. Villeneuve-les-Avignon, chartreuse Notre-Dame-du-Val-de-Bénédiction, church (Gard, France) Avignon, Petit Palais Museum (Vaucluse, France) - Invent.N 80 France, Isère, Notre-Dame-de-Mésage
Tomb: Cardinal Philippe Cabassole, Saint Jacques 14 Around 1372–1377 Bonpas, chartreuse (Vaucluse, France) Avignon, Petit Palais Museum (Vaucluse, France) - Invent.D 95 France, Isère, Notre-Dame-de-Mésage
Statue: St John Baptist 14 Around 1370–1380 Flanders or Northern France ? Chicago Art Institute- Invent. 1947.391 France, Isère, Notre-Dame-de-Mésage
Mourner keeping a book, tomb of Jean de France, the Duke of Berry 15 Middle 15th cent. Bourges, palace of Jean de Berry, Sainte-chapel (destroyed in 1757) (Cher, France) Paris, Louvre Museum, Sculptures Department (France) - Invent. RF 2736 France, Isère, Notre-Dame-de-Mésage
Statue: head of a bearded man 15 Second half 15th cent. ? Paris, Louvre Museum, Sculptures Department (France) - Invent.RF 4108 France, Isère, Notre-Dame-de-Mésage
Statue: Saint Antoine, Arvillard 15 15th cent. Arvillard, chartreuse of Saint-Hugon (?, France) Chambéry, Museum of Fine Arts (Savoie, France) - Invent. D8697 France, Isère, Notre-Dame-de-Mésage
Recumbent effigy: Cardinal Jean de Lagrange 15 After 1402 Avigon, church Saint-Martial (Vaucluse, France) Avignon, Petit Palais Museum (Vaucluse, France) - Invent.N 52 France, Isère, Notre-Dame-de-Mésage
Tomb: Cardinal Jean de Lagrange, Angel of the Annunciation 15 After 1402 Avigon, church Saint-Martial (Vaucluse, France) Avignon, Petit Palais Museum (Vaucluse, France) - Invent.N 60 France, Isère, Notre-Dame-de-Mésage
Tomb: Cardinal Jean de Lagrange, apostle presenting Louis d’Orléans 15 After 1402 Avigon, church Saint-Martial (Vaucluse, France) Avignon, Petit Palais Museum (Vaucluse, France) - Invent.N 54 France, Isère, Notre-Dame-de-Mésage
Tomb: Cardinal Jean de Lagrange, fragment of a head 15 After 1402 Avigon, church Saint-Martial (Vaucluse, France) Avignon, Petit Palais Museum (Vaucluse, France) - Invent.N 227 E France, Isère, Notre-Dame-de-Mésage
Tomb: Cardinal Martin de Salva, Saint Paul 15 After 1403 Bonpas, chartreuse (Vaucluse, France) Avignon, Petit Palais Museum (Vaucluse, France) - Invent.N 69 A France, Isère, Notre-Dame-de-Mésage
Recumbent effigy: Jeanne de Penthièvre 16 First quarter 16th cent. Paris, former convent of the Grands Augustins, chapel of Commynes Paris, Louvre Museum, Sculptures Department (France) - Invent. LP 2665 France, Isère, Notre-Dame-de-Mésage
Recumbent effigy: Renée d’Orléans 16 First quarter 16th cent. Paris, former church of the Célestins Paris, Louvre Museum, Sculptures Department (France) - Invent. RF 3051 France, Isère, Notre-Dame-de-Mésage
Statue: Virgin with child 16 Around 1510–1520 Olivet, former castle of Couasnon (Loiret, France) Paris, Louvre Museum, Sculptures Department (France) - Invent. RF 202 France, Isère, Notre-Dame-de-Mésage
Statue: Tomb of Amiral Chabot: genius, right hand 16 Third quarter 16th cent. Paris, former church of the Célestins Paris, Louvre Museum, Sculptures Department (France) - Invent. ML92 France, Isère, Notre-Dame-de-Mésage
Statue of Saint Stephen: Altarpiece of Tristan de Salazar, 16 Around 1510 ? Sens, Saint-Etienne Cathedral (Yonne, France) Sens, Saint-Etienne Cathedral (Yonne, France) France, Isère, Notre-Dame-de-Mésage
Bas-relief: Dormition of the Virgin 16 Around 1520 Paris, former church Saint-Jacques-de-la-Boucherie Paris, Louvre Museum, Sculptures Department (France) - Invent.RF 428 France, Isère, Notre-Dame-de-Mésage
Tomb: Jean III d’Humières 16 Around 1550 Monchy-Humières church (Oise, France) Paris, Louvre Museum, Sculptures Department (France) - Invent. RF 2471 C France, Isère, Notre-Dame-de-Mésage
Statue: Virgin with the Child 16 16th cent. Breuil, church Notre-Dame (Marne, France) Ecouen Castle,National Museum of the Renaissanc (Val-d’Oise, France) - Invent.E.Cl. 11662 France, Isère, Notre-Dame-de-Mésage
Statue: Virgin Mary 16 16th cent. Provins, church Saint-Ayoul (Seine-et-Marne, France) Provins, church Saint-Ayoul (Seine-et-Marne, France) France, Isère, Notre-Dame-de-Mésage
Statue: Angel as musician with organ 16 16th cent. Provins, church Saint-Ayoul (Seine-et-Marne, France) Provins, church Saint-Ayoul (Seine-et-Marne, France) France, Isère, Notre-Dame-de-Mésage
Group: Saint Anne educating the Virgin Mary 16 16th cent. Sainte-Mesme church (Yvelines, France) Sainte-Mesme church (Yvelines, France) France, Isère, Notre-Dame-de-Mésage
Tomb: Mausoleum of François de Bonne, Constable of Lesdiguières 17 First third 17th cent. Glaizil Castle, in the Champsaur (Hautes-Alpes, France) Museum of Gap (Hautes-Alpes, France) France, Isère, Notre-Dame-de-Mésage
Recumbent effigy: Monsignor Ogier Morizet 15 1435–1440 Cathedral Saint-Jean –Baptiste à Saint-Jean-de-Maurienne Saint-Jean –Baptiste Cathedral in Saint-Jean-de-Maurienne (Savoie, France) France, Savoie, Saint-Jean-de-Maurienne
Statue: Virgin with child 16 First quarter 16th cent. Le Bourget-du-Lac castle, chapel (Savoie, France) Paris, Louvre Museum, Sculptures Department (France) - Invent. RF 1372 France, Savoie, Saint-Jean-de-Maurienne
Sculpted facade of the Jacques d’Amboise palace* 15 End 15th cent. Cluny, palace of Jacques d’Amboise (Saône-et-Loire, France) Cluny, palace of Jacques d’Amboise (Saône-et-Loire, France) France, Burgundy, Berzé-la-Ville
Sculpted facade of the Jacques d’Amboise palace, drill core 3 15 End 15th cent. Cluny, palace of Jacques d’Amboise (Saône-et-Loire, France) Cluny, palace of Jacques d’Amboise (Saône-et-Loire, France) France, Burgundy, Berzé-la-Ville
Recumbent effigy: Pope Urbain V 14 14th cent. Avignon, church Saint-Martial (Vaucluse, France) Avignon, Petit Palais Museum (Vaucluse, France) - Invent.N 231 A1 Avignon France, Provence, Malaucène
recumbent effigy: Pope Urbain V 14 14th cent. Avignon, church Saint-Martial (Vaucluse, France) Avignon, Petit Palais Museum (Vaucluse, France) - Invent.N 231 A3 France, Provence, Malaucène
Statue: Angel of the Annunciation 14 Second third 14th cent. Javernant, church of the Assumption (Aube, France) USA, Cleveland, Museum of Art - Invent.54.387 France, Provence, Malaucène
Statue: Virgin of the Annunciation 14 14th cent. Javernant, church of the Assumption (Aube, France) Paris, Louvre Museum, Sculptures Department (France) - Invent.RF 1661 France, Provence, Malaucène
Statue: Virgin of the Annunciation Restored part Javernant, church of the Assumption (Aube, France) Paris, Louvre Museum, Sculptures Department (France) - Invent. RF 1661 Italy, Tuscany, Volterra region
Statue of Notre-Dame de Bethléem* 14 Last quarter 14th cent. Narbonne Cathedral, chapel Notre-Dame de Bethléem (Aude, France) Narbonne Cathedral, chapel Notre-Dame de Bethléem (Aude, France) Spain, Catalonia, Beuda
High altar (two samples)* 16 1573–1631 Perpignan Cathedral (Pyrénées-Orientales, France) Perpignan Cathedral (Pyrénées-Orientales, France) Spain, Catalonia, Beuda
Altarpiece: Retable de la Déploration* 16 First half 16th cent. Nancy, collegiate churchof Saint-Georges (Meurthe-et-Moselle, France) Nancy, Musée Lorrain (Meurthe-et-Moselle, France) Nonidentified
Statue: Saint Antoine, Brou* 16 Around 1500 Monastery de Brou, rood screen, Bourg-en-Bresse (Ain, France) Monastère Royal de Brou Nonidentified
Bas-relief: tomb of Claude de Guise (black alabaster) 16 Around 1550 Collegiate church of Saint Laurent of the Joinville castle (Haute-Marne, France) Paris, Louvre Museum, Sculptures Department (France) Nonidentified
Bas-relief: tomb of Claude de Guise (white alabaster) 16 Around 1551 Collegiate church of Saint Laurent of the Joinville castle (Haute-Marne, France) Paris, Louvre Museum, Sculptures Department (France) Nonidentified
Statue: Saint holding an open book 16 First quarter 16th cent. ? Paris, Louvre Museum, Sculptures Department (France) - Invent. RF 1637 Nonidentified
Bas-relief: Entombment of Christ 16 16th cent. Chateau-Thierry church (Aisne, France) Ecouen Castle,National Museum of the Renaissanc (Val-d’Oise, France) - Invent.E.Cl. 19385-b Nonidentified
Sculpted facade of the Jacques d’Amboise palace, drill core 2 ? Restored part Cluny, palace of Jacques d’Amboise (Saône-et-Loire, France) Cluny, palace of Jacques d’Amboise (Saône-et-Loire, France) Nonidentified
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*

Artwork reported in ref. 19.

Results and Discussion

Fifteen works of art or parts of sculptural ensembles, ranging from the 14th to 17th centuries, are undoubtedly identified as Triassic alabaster from the English Midlands (Fig. 3). Our sampling strategy mainly included artwork for which English craftsmanship was not stylistically evident; consequently, English material is statistically underrepresented. The only typical “Nottingham School” carving among these samples is a 14th century altar panel that is a fragment of an Arrest of Christ from the Cluny Museum in Paris (20). In contrast, the 15th century “St. Michael striking the Evil” from the Louvre in Paris is attributed to a workshop in the Touraine province of France. These examples illustrate the medieval trade of both carvings and raw alabaster from England. More than half of the samples date from the 16th century, showing the massive export of English alabaster raw materials to France and northern Europe post-1550 in the aftermath of the Protestant iconoclastic crisis. This is illustrated by the isotope analyses (19) of the funeral monument of King Gustaf Vasa of Sweden, sculpted around 1570 by the Flemish artist Willem Boy, and by the monumental high altar of Calais produced by Adam Lottman from Valenciennes in 1624–1628. These findings support Firman’s analysis (21) of an “unprecedented boom in the alabaster trade” lasting 70–80 y from 1580 before going into decline until around 1700.

Fig. 3.

Fig. 3.

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δ34S versus 87Sr/86Sr ratios of alabaster artworks from French, American, Swedish, and English collections from 12th to 17th century, completed with nine samples from our pilot study (19). The data fields are delimited by 2σ confidence ellipses (95% confidence level).

Northern Spain exported heavily to southern Europe (22), but only to the Mediterranean coastal zone in France, notably the Perpignan and Narbonne areas, where alabaster arrived from Beuda by ship (19). Further evidence of local to regional supply is found in Burgundy, where small-scale medieval quarries furnished the decoration of the Jacques d’Amboise Palace in Cluny. Local supply was also evident in Provence and the French Alpine Maurienne region.

The most intriguing result of our study is the great number of non-English carvings with a very homogeneous isotope composition indicative of a French Alpine origin. Virtually all late 14th to early 15th century artworks that are linked to the popes of Avignon (11 artworks), with only one notable exception, fall in an extremely small range of 87Sr/86Sr (0.707796 ± 0.000005 n = 11) and δ34S (15.5 ± 0.1‰ vs. Canyon Diablo Troilite, CDT). This group is complemented with nine artworks from the Louvre Museum (Fig. 4), and six from other collections covering five centuries from the 12th to the 17th century (Fig. 3). The only deposit with a compatible isotope signature is Notre-Dame-de-Mésage (NDM), situated in the western French Alps, southwest of Grenoble. Here, the gypsum quarries are still accessible and alabaster is strongly represented in the local religious architecture. Two artworks in this group are noteworthy. One was collected from a fragment of the funeral chapel of the Counts of Savoy in Hautecombe Abbey. For this sample, a rare and explicit historical source exists detailing the transport of medieval alabaster. The accounting records of the castellany of Vizille (23) for 1336 make specific reference of the transfer of 45 blocks of alabaster on behalf of the Dauphin Humbert II for use by the Counts of Savoy. This exceptional journey began at “Mesatico” (NDM) with a 16-km ride using carts drawn by 110 oxen down to the navigable section of the Isere River. The cargo then proceeded by boat and finished using ox carts again for the remaining 25 km to Hautecombe Abbey, 100 km north of NDM on the shores of Bourget Lake. This source was cited as early as 1722 by Moret de Bourchenu (24), who stated that an alabaster quarry was still active in Mésage. This further proof of quarrying here agrees with our findings characterizing the second noteworthy artwork belonging to this group, the funeral monument of the Constable de Lesdiguières. Indeed, in the 17th century he owned the land where the NDM quarries are situated (25). Four other carvings, mainly 16th–17th century, show similar δ 34S values but higher 87Sr/86Sr ratios and may be attributed to other quarries in the NDM deposits.

Fig. 4.

Fig. 4.

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Carrying of the Cross, alabaster, second quarter 14th century, Paris, Louvre Museum, Sculptures Department (France) - Inventory no. RF 3630. The material of this group was identified as from Notre-Dame-de-Mésage, Isère department, France.

Our study brings to light the extensive geographical distribution and longevity of the French Alpine alabaster industry, rivaling that of the English Midlands. The zone of influence of this French trade encompassed all of the eastern part of France (Fig. 1), crossing the divides of three major river basins: the Rhone, Seine, and Loire. As in the English Midlands (14), river transport was possibly a key to this success with the NDM quarries situated on the banks of the historically (at least temporarily) navigable Romanche River (23), giving access, via the nearby Drac and Isère Rivers, to the Rhone and Avignon. Transloading from ship to ox carts and terrestrial transport, as shown by the Hautecombe example, gave access to the upstream parts of the Rhone basin and other major river basins. We conclude that papal Avignon was almost exclusively supplied with alabaster from NDM and not by sea from Spain via Aigues-Mortes (26).

The only noteworthy Avignon exception is the funeral monument of Pope Urban V (1310–1370) for which we identify the Provencal alabaster of Malaucène as the source, through its highly distinctive isotope signature, strongly enriched in 18O [δ18O of +18.8 ± 0.4‰ vs. standard mean ocean water (SMOW) n = 4, Figs. S1 and S2]. These quarries produced gypsum in the 13th century (27) and the sampled alabaster quarry is mentioned as early as 1458 (27). Malaucène also had a strong historical link with Avignon as it was the summer resort of Pope Clement V, and was situated much closer to the papal city than NDM (43 km compared with 240 km). However, despite the proximity and the availability of good quality of alabaster, NDM was the preferred source. One of the possible reasons is the ease of fluvial transport that was absent at Malaucène. Indeed, the role of the Rhone as principal vector for transporting bulk goods to the Papal Palace has been studied in detail (28). Land transport costs were estimated seven to nine times higher than river transport in the late Roman Empire and five times higher in the 18th century (29), so in medieval times, transport from NDM may have been cost-effective despite the five times longer distance compared with Malaucène.

Fig. S2.

Fig. S2.

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δ34S versus δ18O of alabaster artworks from French, American, Swedish, and English collections from 12th to 17th century, complemented with seven samples from ref. 19. The data fields are delimited by 2σ confidence ellipses (95% confidence level).

Two other sculptures from our corpus are also related to Malaucène, a 14th century annunciation group initially situated in a rural church near Troyes in eastern France. This group has since been separated and the statue of Virgin Mary is conserved by the Louvre in Paris, and the Angel Gabriel by the Cleveland Museum of Arts in the United States. Our multiisotope method proves beyond reasonable doubt their common origin and raw material source. It also identifies a recent restoration, overlooked until now, where part of the base of the statue of the Virgin Mary was replaced by a visually identical but isotopically strongly contrasting material. The restoration alabaster came from the Volterra region in Tuscany, Italy, which was very active both in Etruscan and Roman antiquity and from the 18th to the early 20th centuries. However, this source has not been proved in any of the medieval and Renaissance carvings in western Europe so far analyzed, illustrating the supposed decline of the Volterra quarries until small-scale local use started again in the second half of the 16th century (30).

Our study demonstrates that isotope fingerprinting using S, O, and Sr can uniquely characterize historical sources of alabaster artwork, providing insight into previously unknown patterns of medieval stone trade and the affiliation of artworks to regional workshops or individual artists.

Even if the evidence on transport modes is indirect, our study confirms that fluvial (or marine) transport was generally privileged over terrestrial roads, possibly shorter. Nevertheless, the extension of the diffusion area of some sources (i.e., NDM) has required also the use of terrestrial transport to cross major river basin divides. This is also Cheetham’s conclusion on the alabaster transport in England (14), who states, based on sparse historical records dating back to 1367, that “heavy materials were transported more commonly by road than is often supposed.”

Our method benefits from the strong variations of isotope ratios of S, O, Sr in seawater and the associated evaporites through the Mesozoic (31, 32) and further age-independent contrasts related to varying continental influx and redox conditions in the evaporite basins. The large range of δ34S values of the alabaster deposits from +10.4‰ in the British Permian evaporites to +26.3‰ in the Italian Messinian deposits of Tuscany reflects mainly the evolution of seawater sulfate. Partial isolation of (sub)basins can lead to nonnegligible continental contribution to evaporite formation as shown for the East Midlands (33, 34), where it results in depletion of 34S through sulfide oxidation and recycling of carboniferous evaporites and in more radiogenic 87Sr/86Sr values due to the erosion of the surrounding massifs. Erosion of emerging zones of the crystalline basement would also explain the high 87Sr/86Sr ratios (maximum 0.7096) of the Triassic Burundian deposits, which are well above the highest Mesozoic seawater values of 0.7092 (32).

The observed contrasts in signatures provide a means of forensically investigating restored artworks and forgeries. Extension of the technique to alabaster deposits from eastern Europe and the Mediterranean (35) and to artwork dating back to Antiquity seems promising, given the highly distinctive isotope signatures of Zechstein and Messinian evaporites and the major importance of gypsum alabaster in the art of ancient Mediterranean and Mesopotamian cultures.

SI Materials and Methods

The required minimum quantity for a complete isotope analysis (Sr, S, and O isotopes) using the method described in Kloppmann et al. (19) is less than 20 mg. This corresponds to a tiny flake of around 2 × 2 × 2 mm. Flakes, sampled with a miniature chisel on a noncarved, nonvisible surface of the sculpture (e.g., rear surface or base), were preferred to microdrilling for two reasons: (i) It is possible to detect and correct any treatment or contamination of the surface by manual cleaning under a microscope; (ii) There is less aesthetic impact as the noncarved surfaces frequently have defects such as drilled fixing holes or irregular surfaces allowing discrete sampling to be undertaken.

We strictly avoided any suspected or visible repairs or fixings where gypsum plaster/mortar were present as these are highly contaminant for our method. We also avoided or cleaned, whenever possible, any surface treatments (patina, wax, and painting) to obtain unaltered isotope signatures of fresh material. The samples are crushed, weighed, and slowly dissolved in a closed tube filled with 50 mL of Millipore distilled water at 50 °C in an oven for at least 1 wk. After filtration, the 50 mL solution is divided in three aliquots; two of 5 mL for Sr isotopes and elemental analysis, the 40 mL for sulfur and oxygen isotopes. Sulfates are precipitated as BaSO4 from the filtered solution by adding BaCl2 solution. The precipitate is then filtered off and left to dry and a fraction (∼350 µg) of BaSO4 is mixed with vanadium pentoxide in a tin capsule (36), injected in a flash combustion elemental analyzer (Flash EA) where BaSO4 is reduced to SO2 at 1,700–1,800 °C. The purified SO2 is analyzed for S isotopes by a CF-IRMS: Thermo Delta Plus XP. An aliquot of the BaSO4 (∼200 µg) is placed in a silver capsule, injected in a high-temperature conversion elemental analyzer reactor with a graphite insert at 1,450 °C. The resulting CO is analyzed by CF-IRMS for oxygen isotopes. The isotopic composition of sulfur is expressed in the usual delta notation as a per mil (‰) deviation of the heavy-to-light isotope abundance ratio (34S/32S) in the sample (δ34S), with respect to the CDT standard. Oxygen isotopes (18O/16O) are reported as δ18O with respect to the SMOW standard. Sulfur and oxygen isotopes are measured twice. The external error (1σ), based on repeated measurements of international and in-house standards, is 0.5‰ for δ18O and 0.3‰ for δ34S. Internal errors are systematically lower, if not indicated in Tables S1 and S2.

Chemical purification of Sr is performed using an ion-exchange column (Sr-Spec) before mass analysis according to a method adapted from ref. 37, with total blank <1 ng for the entire chemical procedure. After chemical separation, around 150 ng of Sr is loaded onto a tungsten filament with a tantalum activator and analyzed with a Finnigan MAT262 multicollector TIMS. The measured 87Sr/86Sr ratios are normalized to an 86Sr/88Sr of 0.1194 and then adjusted to the NBS987 standard value of 0.710240. An average internal precision of ±10 × 10−6 (2σm) was currently obtained during this study and the reproducibility of the 87Sr/86Sr ratio measurements was tested through repeated analyses of the NBS 987 standard, for which we obtained a mean value of 0.710248 ± 11 × 10−6 (2σ; n = 372) during the period of analysis (2013–2015).

Acknowledgments

We thank the following curators, museums, collections, and galleries (in France unless stated otherwise) for providing samples and their representatives for their valuable contribution to discussions: Geneviève Bresc and Sophie Jugie from the Louvre Museum in Paris, Dominique Vingtain from the Petit Palais Museum in Avignon, Colleen Snyder from Cleveland Museum of Art (Ohio, USA), Martha Wolff and Cybele Tom from the Chicago Art Institute (Illinois, USA), Damien Berné from the Cluny National Museum of the Moyen-Age in Paris, Thierry Crépin-Leblond from the National Museum of the Renaissance in Ecouen. The Musée Rolin in Autun, the Musée départemental des Hautes-Alpes in Gap, the Musée des Beaux-arts in Chambéry, the Chartreuse of Villeneuve-lez-Avignon, and the Upplandsmuseet in Uppsala (Sweden) kindly provided access to artwork in their collections. Laurine Moreuil and Estelle Saint-Omer contributed to the discussions. The Townships of Cluny and Calais, and the Daniel Katz Gallery in London (UK) and the Chicago Art Institute (USA) provided both samples and financial support. British Gypsum Ltd/Saint Gobain kindly gave access and logistical support for sampling in their gypsum mine at Fauld in Staffordshire (UK). Agela Nestler and colleagues from the Geological Survey of Thüringen (Germany) collected samples of Permian alabaster from south of the Harz Mountains. Olivier Peyre provided precious historical material on the medieval gypsum production in Malaucène and Jacques Galas introduced us to the context of the Malaucène site. Philippe Bertone and Céline Laforest guided us to several other ancient extraction areas in Provence. We also thank Fabio Fratini (geologist, CNR Florence), Felice Tirabasso (quarry manager in Castellina Marittima for the Knauf company), and Gabriele Marasco in Volterra for their help collecting samples at historical alabaster extractions in Tuscany (Italy). Anthony Cooper publishes with permission of the Director of the British Geological Survey. This article was greatly improved by reviews by Jane Evans and Stephen Parry of the British Geological Survey, Rowena Stead of the French Geological Survey BRGM, and two anonymous reviewers. This study was cofunded by the Louvre Museum/Fondation des Science du Patrimoine, by the BRGM (Bureau de Recherches Géologiques et Minières), the Centre Interdisciplinaire de Conservation et Restauration du Patrimoine (CICRP), the Laboratoire de Recherche des Monuments Historiques (CRC-LRMH), and Idex Sorbonne Universités Pour l’Enseignement et la Recherche.

Footnotes

The authors declare no conflict of interest.

This article is a PNAS Direct Submission.

2Retired.

This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1707450114/-/DCSupplemental.

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