Pyrolysis-compound specific isotope analysis (Py-CSIA) of ... · Pyrolysis-compound specific...
1
Layla M. San-Emeterio (1), José M. de la Rosa (1), Nicasio T Jiménez-Morillo (2), and José A. González-Pérez (1) (1) Consejo Superior de Investigaciones Científicas (CSIC), Instituto de Recursos Naturales y Agrobiología de Sevilla (IRNAS), Seville, Spain ([email protected]), (2) Laboratório HERCULES - Herança Cultural, Estudos e Salvaguarda, Universidade de Évora. ► Cultural heritage hold an artistic, social and economic value. ► Isotopic analysis provide a better understanding of decay and deterioration. ► This information allows to design effective conservation methodologies, as well as ensure long-term management strategies. ► Accurate isotopic characterization of organic materials, including polymers and biopolymers used in the past as construction, supporting or protective materials, will help to ameliorate the conservation practices for controlling deterioration and preventing key and current issues such as pollution, climate change. ✓ Small sample size: only a few miligrams of a single sample are required for a determination. ✓ Time saving: no pre-treatment nor extraction procedures are generally needed. ✓ Less handling: avoid experimental errors. ✓ Good reproducibility. ✓ Complex materials or mixtures (including biopolymers), with varying structures and origins can be analyzed. ✓ By using Py-CSIA, key compounds of heritage material for their conservation can be characterized. ✓ Py-CSIA results in an innovative approach in heritage science, providing tools for decisión-makers in this field. Py - GC - C/TC - IRMS : provides isotopic information (δ 13 C δD δ 18 O δ 15 N) A double-shot/micro-furnace pyrolyzer (Frontier Laboratories, model 3030D). Individual volatile pyrolysis products separated by GC are directed to GC-Isolink System with combustion (C and N) and pyrolysis (H or O) micro-furnaces. Coupled to isotope ratio mass spectrometer, IRMS (Thermo Delta V Advantage) via a ConFlo IV universal interface unit. Gas chromatograph (Trace Ultra GC system). Pyrolysis - compound specific isotope analysis ( Py - CSIA) of polymers and biopolymers: possible applications in heritage conservation BACKGROUND CONTACT: ACKNOLEGMENTS: The authors wish to thank to Dr. Ana Z. Miller for encouraging the presentation of this work. This research has been funded by the Spanish Gov. ‘Ministerio de Ciencia , Innovación y Universidades’ under grant ref. BES–2017–079811 . Project CGL 2016 -78937 –Co-financed by FEDER Funds . Thanks to Desiré Monis and Alba Carmona for technical assistance METHODOLOGY: OUR INSTRUMENTS HIGHLIGHTS Py-CSIA BIOPOLYMERS: FINGERPRINTINGS © Ana Z. Miller Vilar de Frades Monastery (Barcelos, Portugal) APPLICATIONS δ15N • Trophic levels. • Evaluations of both diet pattern and provenances [3]. • Elucidate agricultural production means. • Pollution tracers (atmospheric contamination). δ13C • Diet for humans and nutritional ecology [3]. • Trace of ancient pottery: degraded lipids preserved [4]. • Paleoenvironment and climate changes: e.g. dendrology. • Identification of dominant mode of rock formation: e.g. origin of carbonates [5] . δ2H • Both elements are linked to water; therefore, they are complimentary. • Contraints on environmental processes: e.g. water scarcity in plants. • Migration among humans, animals and plants: biogeography. • Water uptake, which depends on altitude and latitude. • Thus, it can be used to trace a geographic origin of organic materials [6]. • Paleo-thermometry. δ18O Pyrolysis-compound specific isotope analysis (Py-CSIA) is a relatively novel analytical technique able to provide identification of organic compounds in different complex matrices [1, 2]. This technique also offer additional valuable information about nature and origin of the materials based on their isotopic composition. With this technique it is possible to make direct isotopic measurements of major organic matter elements (i.e. δ13C, δD, δ15N and also δ18O) of specific compounds. +11.2 ‰ +17.4 ‰ +15.3 ‰ +16.3 ‰ δ 15 N BULK = +12.2±0.1 ‰ (Air-N 2 ) +10.4 ‰ Py- 15 N-CSIA +18.2 ‰ δ 15 N CSIA = +15.0±3.0 ‰ (Air-N 2 ) Py- 13 C-CSIA −24.6 ‰ −22.5 ‰ −27.7 ‰ −27.8 ‰ −27.8 ‰ δ 13 C BULK = −22.6±0.2 ‰ (VPDB) −24.2 ‰ −23.0 ‰ δ 13 C CSIA =−25.4±2.3 ‰ (VPDB) CASE 1: Keratin (protein) 1 2 4 3 5 6 8 7 9 11 12 13 14 15 16 17 18 20 21 22 23 24 25 26 27 29 30 31 32 33 34 36 37 38 39+40 41 42 43 44 28 35 10 Py-GC/MS Indole Pro-Pro DKP Alkylamide C 22 C 24 C 26 Cholesterol FA C 18 Me-Indole Pro-Leu DKP 4 6 8 10 12 14 16 18 20 22 24 Time (min)--> 26 2 9 1 3 5 7 11 12 15 Alk Alk Sterol Alk POLYSACCHARIDS PHENOL LIGNIN LIKE: Polyphenolic domain FATTY ACIDS LIPIDS: Polyaliphatic domain FAME 2 4 6 8 10 13 FA Alk FA 14 Alk FA FA Alk FA Alk Alk FA Alk Alk 16 Alk Sterol Alk FA m/z 46 m/z 45 m/z 44 −24.6 −27.4 −27.8 −28.1 −27.0 −26.3 −27.3 −27.5 −26.3 −27.2 −27.4 −27.6 −27.3 −27.8 −27.7 −27.6 −27.2 −26.3 −28.0 −27.3 −27.7 −27.7 −28.3 −28.1 −28.1 −28.1 −28.3 −28.5 −28.1 −28.2 −27.6 −28.0 −30.0 −29.0 −28.0 −28.0 δ 13 C BULK = −27.2 ± 0.02 ‰ (VPDB) δ 13 C CSIA = −27.5 ± 1.4 ‰ (VPDB) CASE 2: Suberin (cork oak) Py- 13 C-CSIA Py-GC/MS 4 6 8 10 12 14 16 18 20 22 24 Time (min)--> 26 2 Py-GC/MS CASE 3: Lignin (wood) m/z 46 m/z 45 m/z 44 Py- 13 C-CSIA -29.7 -29.7 -29.4 -29.7 -30.5 -29.3 -29.0 -28.7 - 28.6 - 25.0 7 4 3 1 2 5 6 8 9 10 4 6 8 10 12 14 16 18 20 22 24 Time (min)--> 26 2 δ 13 C BULK = −30.54 ± 0.03 ‰ (VPDB) δ 13 C CSIA = −30.43 ± 1.5 ‰ (VPDB) REFERENCES: [1] González‐Pérez et al. (2016). Compound‐specific stable carbon isotopic signature of carbohydrate pyrolysis products from C3 and C4 plants. Journal of the Science of Food and Agriculture, 96(3), 948-953. [2] González-Pérez et al.. (2015). Pyrolysis-gas chromatography–isotope ratio mass spectrometry of polyethylene. Journal of Chromatography A, 1388, 236-243. [3] Gil et al. (2011). Stable isotopes and human diet in central western Argentina. Journal of Archaeological Science, 38(7), 1395-1404. [4 ] Mottram et al.. (1999). New chromatographic, mass spectrometric and stable isotope approaches to the classification of degraded animal fats preserved in archaeological pottery. Journal of Chromatography A, 833(2), 209-221. [5] Tambakopoulos, D., & Maniatis, Y. (2017). The marble of the Cyclades and its use in the Early Bronze Age. Early cycladic sculpture in context. Oxbow: Oxford and Philadelphia, 468-82. [6] von Holstein, I. C., & Makarewicz, C. A. (2016). Geographical variability in northern European sheep wool isotopic composition (δ13C, δ15N, δ2H values). Rapid Communications in Mass Spectrometry, 30(12), 1423-1434. . Check out our lab’s updates in ResearchGate Py - GC/ MS: provides structural information A conventional Py-GC/MS system (F. Labs 2020i ) + Agilent MSD 6890N) Layla M. San Emeterio | [email protected] Ph.D. Student POLYSACCHARIDS LIGNIN GUAYACIL UNIT (G) LIGNIN SYRINGIL UNIT (S) LIPIDS: fatty acids and wood extractives
Transcript of Pyrolysis-compound specific isotope analysis (Py-CSIA) of ... · Pyrolysis-compound specific...
Layla M. San-Emeterio (1), José M. de la Rosa (1), Nicasio T Jiménez-Morillo (2), and José A. González-Pérez (1)(1) Consejo Superior de Investigaciones Científicas (CSIC), Instituto de Recursos Naturales y Agrobiología de Sevilla (IRNAS), Seville, Spain ([email protected]),
(2) Laboratório HERCULES - Herança Cultural, Estudos e Salvaguarda, Universidade de Évora.
► Cultural heritage hold an artistic, social and economic value.
► Isotopic analysis provide a better understanding of decay and deterioration.
► This information allows to design effective conservation methodologies, as
well as ensure long-term management strategies.
► Accurate isotopic characterization of organic materials, including polymers
and biopolymers used in the past as construction, supporting or protective
materials, will help to ameliorate the conservation practices for controlling
deterioration and preventing key and current issues such as pollution, climate
change.
✓ Small sample size: only a few miligrams of a single sample are required for a
determination.
✓ Time saving: no pre-treatment nor extraction procedures are generally needed.
✓ Less handling: avoid experimental errors.
✓ Good reproducibility.
✓ Complex materials or mixtures (including biopolymers), with varying structures
and origins can be analyzed.
✓ By using Py-CSIA, key compounds of heritage material for their conservation can
be characterized.
✓ Py-CSIA results in an innovative approach in heritage science, providing tools for
decisión-makers in this field.
Py-GC-C/TC-IRMS: provides isotopic information (δ13C δD δ18O δ15N)
A double-shot/micro-furnace pyrolyzer
(Frontier Laboratories, model 3030D).
Individual volatile pyrolysis products
separated by GC are directed to GC-Isolink
System with combustion (C and N) and
pyrolysis (H or O) micro-furnaces.
Coupled to isotope ratio mass spectrometer,
IRMS (Thermo Delta V Advantage) via a ConFlo
IV universal interface unit.
Gas chromatograph (Trace Ultra GC system).
Pyrolysis-compound specific isotope analysis (Py-CSIA) of polymers and biopolymers: possible applications in heritage conservation
BACKGROUND
CONTACT:
ACKNOLEGMENTS:The authors wish to thank to Dr. Ana Z. Miller for encouraging the presentation of this work.
This research has been funded by the Spanish Gov. ‘Ministerio de Ciencia , Innovación y Universidades’ under grant ref. BES–2017–079811 . Project
CGL 2016 -78937 –Co-financed by FEDER Funds . Thanks to Desiré Monis and Alba Carmona for technical assistance
METHODOLOGY: OUR INSTRUMENTS
HIGHLIGHTS
Py-CSIA BIOPOLYMERS: FINGERPRINTINGS
© Ana Z. Miller
Vilar de Frades Monastery (Barcelos, Portugal)
APPLICATIONS
δ15N
• Trophic levels.
• Evaluations of both diet pattern and provenances [3].
• Elucidate agricultural production means.
• Pollution tracers (atmospheric contamination).
δ13C
• Diet for humans and nutritional ecology [3].
• Trace of ancient pottery: degraded lipids preserved [4].
• Paleoenvironment and climate changes: e.g. dendrology.
• Identification of dominant mode of rock formation: e.g. origin of
carbonates [5] .
δ2H• Both elements are linked to water; therefore, they are complimentary.
• Contraints on environmental processes: e.g. water scarcity in plants.
• Migration among humans, animals and plants: biogeography.
• Water uptake, which depends on altitude and latitude.
• Thus, it can be used to trace a geographic origin of organic materials [6].
• Paleo-thermometry.δ18O
Pyrolysis-compound specific isotope analysis (Py-CSIA) is a relatively novel analytical
technique able to provide identification of organic compounds in different complex
matrices [1, 2]. This technique also offer additional valuable information about nature
and origin of the materials based on their isotopic composition. With this technique it
is possible to make direct isotopic measurements of major organic matter elements
(i.e. δ13C, δD, δ15N and also δ18O) of specific compounds.
+11.2 ‰
+17.4 ‰
+15.3 ‰
+16.3 ‰
δ15NBULK= +12.2±0.1 ‰ (Air-N2)
+10.4 ‰
Py-15N-CSIA
+18.2 ‰
δ15NCSIA= +15.0±3.0 ‰ (Air-N2)
Py-13C-CSIA
−24.6 ‰
−22.5 ‰
−27.7 ‰ −27.8 ‰
−27.8 ‰
δ13CBULK= −22.6±0.2 ‰ (VPDB)
−24.2 ‰
−23.0 ‰
δ13CCSIA =−25.4±2.3 ‰ (VPDB)
CA
SE 1
: K
era
tin
(pro
tein
)
1 2 43
5 6
8
79
11
12
13
14
15 1617
18 20
21
22
23
24 25
26
27
29
3031
32 33 34 36
3738
39+40
41
42
43
4428
3510
Py-GC/MS
IndolePro-Pro DKP
Alkylamide C22 C24 C26
CholesterolFA C18
Me-Indole
Pro-Leu DKP
4 6 8 10 12 14 16 18 20 22 24
Time (min)-->
262
9
1 3
5 7
11 12
15 Alk
Alk
Sterol
Alk
POLYSACCHARIDS
PHENOL
LIGNIN LIKE: Polyphenolic domain
FATTY ACIDS
LIPIDS: Polyaliphatic domain
FAME
2
4 6
8
10
13 FA
Alk
FA
14
Alk
FAFA
Alk
FA
AlkAlk
FA
Alk Alk
16
Alk
Sterol
Alk
FA
m/z 46
m/z 45
m/z 44
−24.6
−27.4
−27.8
−28.1
−27.0
−26.3
−27.3
−27.5
−26.3
−27.2
−27.4 −
27.6
−27.3
−27.8
−27.7
−27.6
−27.2
−26.3
−28.0
−27.3
−27.7
−27.7
−28.3
−28.1
−28.1
−28.1
−28.3
−28.5
−28.1
−28.2
−27.6
−28.0
−30.0
−29.0
−28.0
−28.0
δ13CBULK = −27.2 ± 0.02 ‰ (VPDB)
δ13CCSIA = −27.5 ± 1.4 ‰ (VPDB)
CA
SE 2
: Suberi
n(c
ork
oak)
Py-13C-CSIA
Py-GC/MS
4 6 8 10 12 14 16 18 20 22 24
Time (min)-->
262
Py-GC/MS
CA
SE 3
: Lig
nin
(wood)
m/z 46
m/z 45
m/z 44Py-13C-CSIA
-29.7
-29.7
-29.4
-29.7
-30.5
-29.3
-29.0-2
8.7
-28.6
-25.0
7
43
1
2
5
6
8
9
10
4 6 8 10 12 14 16 18 20 22 24
Time (min)-->
262
δ13CBULK = −30.54 ± 0.03 ‰ (VPDB)
δ13CCSIA = −30.43 ± 1.5 ‰ (VPDB)
REFERENCES:[1] González‐Pérez et al. (2016). Compound‐specific stable carbon isotopic signature of carbohydrate pyrolysis products from C3 and C4 plants. Journal of the Science of Food and Agriculture, 96(3), 948-953.
[2] González-Pérez et al.. (2015). Pyrolysis-gas chromatography–isotope ratio mass spectrometry of polyethylene. Journal of Chromatography A, 1388, 236-243.
[3] Gil et al. (2011). Stable isotopes and human diet in central western Argentina. Journal of Archaeological Science, 38(7), 1395-1404.
[4] Mottram et al.. (1999). New chromatographic, mass spectrometric and stable isotope approaches to the classification of degraded animal fats preserved in archaeological pottery. Journal of Chromatography A, 833(2), 209-221.
[5] Tambakopoulos, D., & Maniatis, Y. (2017). The marble of the Cyclades and its use in the Early Bronze Age. Early cycladic sculpture in context. Oxbow: Oxford and Philadelphia, 468-82.
[6] von Holstein, I. C., & Makarewicz, C. A. (2016). Geographical variability in northern European sheep wool isotopic composition (δ13C, δ15N, δ2H values). Rapid Communications in Mass Spectrometry, 30(12), 1423-1434.
.
Check out our lab’s updates
in ResearchGate
Py-GC/MS: provides structural information
A conventional Py-GC/MS system (F. Labs 2020i )
+ Agilent MSD 6890N)
Layla M. San Emeterio | [email protected]
Ph.D. StudentPOLYSACCHARIDS
LIGNIN GUAYACIL UNIT (G)
LIGNIN SYRINGIL UNIT (S)
LIPIDS: fatty acids and wood extractives
