[1] Le Brun-Ricalens, Foni, and Jean-Guillaume Bordes. (2007) [2] Conard, Nicholas J. Nature 426.6968 (2003): 830-832. [3] Conard, Nicholas J., Maria Malina, and Susanne C. Münzel. Nature 460.7256 (2009): 737-740. ◆ Comparison of diagenetic processes imaging at New AGLAE and at PUMA ◆ Conclusion Contact: [email protected] ◆ Study of prehistoric ivories ◆ Imaging set-up at New AGLAE / C2RMF and at PUMA / SOLEIL [4] Albéric, Marie. Diss. Paris 6, 2014. [5] Reiche, Ina, et al. Angewandte Chemie International Edition 57.25 (2018): 7428-7432. • Period of interest: Aurignacian corresponding to the early Paleolithic era (43 000 – 33 000 BP) • Appearance of Homo sapiens in western Europe and beginning of his coexistence with Homo neanderthalensis Remarkable characteristics of Hohle Fels site: • Discovery of the earliest example of expressly human figurative art (Venus figurine) and some of the earliest musical instruments ever found (ivory and bone flutes) [2, 3] • Holhe Fels site successively occupied by Homo neanderthalensis and then by Homo sapiens In this work we deal with the following two research questions which are raised in the investigation of Paleolithic ivories and bones: - How is ivory degrading over time ? (Diagenetic process) - What are the persistent signatures of early Paleolithic ivories ? (Provenancing) 1 st axis of this work PUMA : • Microbeam 2D imaging station - 3 x 5 µm 2 spot size - 4 to 22 keV energy incident beam • Analysis techniques: - X-ray fluorescence (XRF) - X- ray absorption (XANES) New AGLAE: Combined 3MeV Proton micro-PIXE/PIGE/RBS* imaging set-up Study of ivory sample AI-HF-01 XRF Fe mapping 1.5 mm x 1.5 mm • Comparison of the imaging results obtained by PIXE at New AGLAE and by Synchrotron XRF at PUMA • Study of three specific elements: P (specific to ivory), Fe (element enriched due to diagenesis) and Zn (element weakly dependent on diagenesis) [5] ◆ Additional analysis at PUMA: XANES • Chemical information for each element obtained by XANES • Same chemical state for Fe in different spots of sample AI-HF-01 (same spectra) • Possibility to fit with a linear combination of standards ● New AGLAE and PUMA provide complementary non- invasive tools for the total investigation of the chemical composition of Palaeolithic ivory on major minor and trace element level. ● Chemical imaging of light to heavy elements even on trace level allow for determining reliable proxies for provenancing and diagenetic pathways. Distribution of Aurignacian technocomplex in Europe and Middle east [1] Microscope image (PUMA) 1.3 mm x 1.3 mm Venus of Hohle Fels, South-west of Germany Sites containing Aurignacian ivories located in western Europe and analysed in this project Study of mammoth ivories and bones coming from Hohle Fels site, provided by N. Conard et al., Univ. of Tübingen, Germany ◆ Chemical composition of ivory Shift Space between the NH2 and COOH ends Ivory is a hierarchically biocomposite material including an organic phase (25-35%) and a mineral phase (55-65%). [4] Organic phase: collagen organized in fibrils Mineral phase: hydroxyapatite Ca 10 (PO 4 ) 6 OH 2 rich in Mg + H 2 O (~10%) Mineralization of fibrils Additional trace elements: F, Na, Al, Si, S, Cl, Sr, Cr, Mn, Fe, Cu, Zn, Sr, Ba and Pb Strong diversity of elements present (light and heavy) in Paleolithic ivories make their study relevant to highlight the potential of complementary analyses and imaging at New AGLAE / C2RMF and at PUMA / SOLEIL. 2 nd axis of this work - 2 MV tandem accelerator (Pelletron 6SDH-2) - high spatial resolution (6 x 3 µm 2 ) of a large analyzed area until 20 x 20 cm 2 *PIXE: Particle-Induced X-ray emission PIGE: Particle-Induced Gamma-ray emission RBS: Rutherford Back Scattering Counts Counts XRF Zn mapping 1.5 mm x 1.5 mm PUMA XRF mapping: - Total Duration: 11 h 19 mins - Dwell time/pixel: 1 sec - Beam flux: 10 10 photons/sec - Beam spot size: 5 µm x 5 µm Microscope image (New AGLAE) 1.3 mm x 1.5 mm Counts PIXE Fe mapping 1.3 mm x 1.5 mm Counts PIXE P mapping 1.3 mm x 1.5 mm Counts PIXE Zn mapping 1.3 mm x 1.5 mm New AGLAE PIXE mapping: - Total Duration: 1 h 11 mins - Total charge : 16.7 µC - Beam flux: 2.8 x 10 10 photons/sec - Beam spot size: 50 µm x 50 µm • Fe located mainly in the crack on the contrary of P and of Zn confirming previous studies of ivory diagenesis • Similar results obtained for Fe with PUMA and New AGLAE • No observation of P with PUMA XRF set-up, poor mapping of Zn with New AGLAE PIXE set-up • Lower number of counts by PIXE due to the use of an Al filter and to the difference of fluorescence quantum yield between proton-induced emission (New AGLAE) and photon-induced emission (PUMA) Counts PIGE F mapping 1.3 mm x 1.5 mm • Detection of light elements such as F, Na, Mg, Al and P thanks to PIGE analysis • Importance of F for the assessment of diagenetic processes and for relative dating • 800 ppm of F detected in AI-HF-01 PIGE spectrum of sample AI-HF-01 RBS spectrum of sample AI-HF-06 (cross-section of another ivory sample) • Detection of light elements such as C, N and O possible thanks to RBS analysis • Importance of C to determine the presence of remaining organic phase (collagen) Ca O C He 1 2 3 Microscope image and XRF Fe mapping of AI-HF-01 with XANES Fe measurements spots Normalized XANES Fe spectra Normalized XANES Fe spectra of AI-HF-01 versus a linear combination fit of goethite FeO(OH) (0.249 weighted) and jacobsite MnFe 2 O 4 (0.751 weighted) ◆ Additional analysis at New AGLAE: PIGE and RBS Acknowledgements : We thank Claire Heckel, Nicolas Conard, Harald Floss and Sibylle Wolf from Uni Tübingen for having provided the ivory samples and Angélique Rouquié for the technical support on the PUMA beamline. We acknowledge the measurement time allowance by the synchrotron SOLEIL at the PUMA beamline through the proposal number 20200168. The ion beam analysis experiments were performed at the New AGLAE facility (ANR - 10 - EQPX 22). Laurent Tranchant 1 , Katharina Müller 2 , Quentin Lemasson 3, 4 , Laurent Pichon 3, 4 , Claire Pacheco 3, 4 , Sebastian Schoeder 1 and Ina Reiche 3- 5 1 Synchrotron SOLEIL, BP 48 Saint-Aubin, 91192 Gif-sur-Yvette, France 2 IPANEMA, USR3641, CNRS, Ministère de la Culture et de la Communication, Université de Versailles Saint-Quentin-en-Yvelines, Université Paris-Saclay, 91192 Gif-sur-Yvette, France 3 Centre de recherche et de restauration des musées de France, C2RMF, Palais du Louvre, 75001 Paris, France 4 Fédération de recherche NewAGLAE, FR3506 CNRS/Ministère de la Culture/UPMC, Palais du Louvre, 75001 Paris, France 5 PSL Université, ENSCP, Institut de recherche de Chimie Paris, UMR 8247 CNRS, PCMTH team, 75005 Paris, France Prehistoric ivories. Potential of complementary analyses and imaging at New AGLAE / C2RMF and at PUMA / SOLEIL PIGE detector RBS external detector Microscope PIXE high energy SDD detector PIXE high energy SDD detector Beam PIXE high energy SDD detector PIXE low energy SDD detector with deflecting magnet and He flow
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[1] Le Brun-Ricalens, Foni, and Jean-Guillaume Bordes. (2007)[2] Conard, Nicholas J. Nature 426.6968 (2003): 830-832.[3] Conard, Nicholas J., Maria Malina, and Susanne C. Münzel. Nature 460.7256 (2009): 737-740.
◆ Comparison of diagenetic processes imaging at New AGLAE and at PUMA
◆ Conclusion
Contact: [email protected]
◆ Study of prehistoric ivories
◆ Imaging set-up at New AGLAE / C2RMF and at PUMA / SOLEIL
[4] Albéric, Marie. Diss. Paris 6, 2014.[5] Reiche, Ina, et al. Angewandte Chemie International Edition 57.25 (2018): 7428-7432.
• Period of interest: Aurignacian correspondingto the early Paleolithic era (43 000 – 33 000BP)
• Appearance of Homo sapiens in westernEurope and beginning of his coexistence withHomo neanderthalensis
Remarkable characteristics of Hohle Fels site:• Discovery of the earliest example of expressly
human figurative art (Venus figurine) and some ofthe earliest musical instruments ever found (ivoryand bone flutes) [2, 3]
• Holhe Fels site successively occupied by Homoneanderthalensis and then by Homo sapiens
In this work we deal with the following two research questions which are raised in theinvestigation of Paleolithic ivories and bones:- How is ivory degrading over time ? (Diagenetic process)- What are the persistent signatures of early Paleolithic ivories ? (Provenancing)
1st axis of this work
PUMA:• Microbeam 2D imaging station
- 3 x 5 µm2 spot size- 4 to 22 keV energy incident beam
• Analysis techniques:- X-ray fluorescence (XRF)- X- ray absorption (XANES)
New AGLAE:Combined 3MeV Protonmicro-PIXE/PIGE/RBS*imaging set-up
Study of ivory sample AI-HF-01
XRF Fe mapping1.5 mm x 1.5 mm
• Comparison of the imaging results obtained by PIXE at New AGLAE and by Synchrotron XRF at PUMA
• Study of three specific elements: P (specific to ivory), Fe (element enriched due to diagenesis) and Zn (elementweakly dependent on diagenesis) [5]
◆ Additional analysis at PUMA: XANES
• Chemical information for each element obtained by XANES• Same chemical state for Fe in different spots of sample AI-HF-01 (same spectra)• Possibility to fit with a linear combination of standards
● New AGLAE and PUMA provide complementary non-invasive tools for the total investigation of thechemical composition of Palaeolithic ivory on majorminor and trace element level.
● Chemical imaging of light to heavy elements even ontrace level allow for determining reliable proxies forprovenancing and diagenetic pathways.
Distribution of Aurignacian technocomplex in Europe and Middle east [1]
Microscope image(PUMA)
1.3 mm x 1.3 mm
Venus of Hohle Fels,South-west of Germany
Sites containing Aurignacian ivories located in western Europe and analysed in this project
Study of mammoth ivories and bones coming from Hohle Fels site, provided by N. Conard et al., Univ. of Tübingen, Germany
◆ Chemical composition of ivory
Shift
Space between the NH2 and COOH ends
Ivory is a hierarchically biocomposite material including an organic phase (25-35%) and a mineralphase (55-65%). [4]
Organic phase: collagen organized in fibrils Mineral phase: hydroxyapatiteCa10(PO4)6OH2 rich in Mg
+ H2O (~10%)
Mineralization of fibrils
Additional trace elements: F, Na, Al, Si, S, Cl, Sr, Cr, Mn, Fe, Cu, Zn, Sr, Ba and Pb
Strong diversity of elements present (light and heavy) in Paleolithic ivories make their studyrelevant to highlight the potential of complementary analyses and imaging at New AGLAE /C2RMF and at PUMA / SOLEIL.
2nd axis of this work
- 2 MV tandem accelerator (Pelletron 6SDH-2)- high spatial resolution (6 x 3 µm2) of a large analyzed area until 20 x 20 cm2
*PIXE: Particle-Induced X-ray emissionPIGE: Particle-Induced Gamma-ray emissionRBS: Rutherford Back Scattering
Counts
Counts
XRF Zn mapping1.5 mm x 1.5 mm
PUMA XRF mapping:- Total Duration: 11 h 19 mins- Dwell time/pixel: 1 sec- Beam flux: 1010 photons/sec- Beam spot size: 5 µm x 5 µm
Microscope image(New AGLAE)
1.3 mm x 1.5 mm
Counts
PIXE Fe mapping1.3 mm x 1.5 mm
Counts
PIXE P mapping1.3 mm x 1.5 mm
Counts
PIXE Zn mapping1.3 mm x 1.5 mm
New AGLAE PIXE mapping:- Total Duration: 1 h 11 mins - Total charge : 16.7 µC- Beam flux: 2.8 x 1010 photons/sec- Beam spot size: 50 µm x 50 µm
• Fe located mainly in the crack on the contrary of P and of Zn confirming previous studies of ivory diagenesis• Similar results obtained for Fe with PUMA and New AGLAE• No observation of P with PUMA XRF set-up, poor mapping of Zn with New AGLAE PIXE set-up• Lower number of counts by PIXE due to the use of an Al filter and to the difference of fluorescence quantum yield
between proton-induced emission (New AGLAE) and photon-induced emission (PUMA)
Counts
PIGE F mapping1.3 mm x 1.5 mm
• Detection of light elements such as F, Na,Mg, Al and P thanks to PIGE analysis
• Importance of F for the assessment ofdiagenetic processes and for relativedating
• 800 ppm of F detected in AI-HF-01
PIGE spectrum of sample AI-HF-01
RBS spectrum of sample AI-HF-06 (cross-section of another ivory sample)
• Detection of light elements such as C, Nand O possible thanks to RBS analysis
• Importance of C to determine thepresence of remaining organic phase(collagen)
Ca
O
C
He
12 3
Microscope image and XRF Fe mapping of AI-HF-01 with XANES Fe measurements spots Normalized XANES Fe spectra Normalized XANES Fe spectra of AI-HF-01 versus a
linear combination fit of goethite FeO(OH) (0.249 weighted) and jacobsite MnFe2O4
(0.751 weighted)
◆ Additional analysis at New AGLAE: PIGE and RBS
Acknowledgements: We thank Claire Heckel, Nicolas Conard, Harald Floss and Sibylle Wolf from Uni Tübingen for having provided the ivorysamples and Angélique Rouquié for the technical support on the PUMA beamline. We acknowledge the measurement time allowance by thesynchrotron SOLEIL at the PUMA beamline through the proposal number 20200168. The ion beam analysis experiments were performed at theNew AGLAE facility (ANR - 10 - EQPX 22).
Laurent Tranchant1, Katharina Müller2, Quentin Lemasson3, 4, Laurent Pichon3, 4, Claire Pacheco3, 4, Sebastian Schoeder1
and Ina Reiche3- 5
1 Synchrotron SOLEIL, BP 48 Saint-Aubin, 91192 Gif-sur-Yvette, France2 IPANEMA, USR3641, CNRS, Ministère de la Culture et de la Communication, Université de Versailles Saint-Quentin-en-Yvelines, Université Paris-Saclay, 91192 Gif-sur-Yvette, France 3 Centre de recherche et de restauration des musées de France, C2RMF, Palais du Louvre, 75001 Paris, France
4 Fédération de recherche NewAGLAE, FR3506 CNRS/Ministère de la Culture/UPMC, Palais du Louvre, 75001 Paris, France5 PSL Université, ENSCP, Institut de recherche de Chimie Paris, UMR 8247 CNRS, PCMTH team, 75005 Paris, France
Prehistoric ivories. Potential of complementary analyses and imaging at New AGLAE / C2RMF and at PUMA / SOLEIL
PIGE detector
RBS external detector Microscope
PIXE highenergy SDDdetector
PIXE highenergy SDDdetector
BeamPIXE high energySDD detector
PIXE lowenergy SDDdetectorwithdeflectingmagnet andHe flow
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