Organic Remains in Early Christian Egyptian Metal Vessels: Investigation with Fourier Transform Infrared Spectroscopy and Gas Chromatography–Mass Spectrometry
Abstract
:1. Introduction
2. Experimental Procedures
2.1. Fourier Transform Infrared Spectroscopy
2.2. FTIR Analysis of Powder Samples in KBr Discs
2.3. Solvent Extraction for FTIR Analysis
2.4. Gas Chromatography–Mass Spectrometry
2.4.1. Sample Preparation for GC-MS
2.4.2. GC-MS Analysis
3. Results and Discussion
3.1. Fourier Transform Infrared Spectroscopy
3.1.1. Powder Samples
3.1.2. Solvent-Extracted FTIR Results
3.2. Solvent-Extraction-μFTIR
3.3. Gas Chromatography–Mass Spectrometry
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Acknowledgments
Conflicts of Interest
Abbreviations
MAG | Mono-fatty Acyl Glycerols |
DAG | Di-fatty Acyl Glycerols |
TAG | Tri-fatty Acyl Glycerols |
DiFA | diacids (dicarboxylic acids) |
FA | Fatty Acids |
FAMS | Fatty Acids Metal Salts |
FTIR | Fourier Transform Infra-Red spectroscopy |
GC-MS | gas chromatography–mass spectrometry |
SE-FTIR | Solvent-Extracted FTIR |
SE-μFTIR | Solvent-Extracted microscopy-FTIR |
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Sample Number; Description | KBr-FTIR Results | Organics through Solvent-Extracted FTIR Results | Organics through GC-MS |
---|---|---|---|
11544 Remain from interior | Inorganics a: Calcite (l.a.), silicates, SiO2 (r); oxalates. Organics b: carboxylic acids, metal soaps (l.a.), esters. | Methanol: glyceryl mono- and diesters, fatty monoacids, diacids, and carboxylates (metal soaps). Acetone: acylglycerols (l.a.), saturated fatty monoacids (r.), anhydrides/lactones. Dichloromethane: acylglycerols, short/mid-chain fatty monoacids (r.) | FAs C16:0 (r.) and C18:0; diacids C9di and C13di; Even-numbered sat. FAs C8:0–C24:0;Odd-numbered sat. FAs: C9:0 and C15:0; Unsat. FAs: C16:1 and C18:1.Oxo- and hydroxy-FAs C6, C7, C8. Dihydroxy-FAs C18(diOH) and C22(diOH). Diacid series (C4di–C14di). C16- and C18-MAG (l.a.). Beta-sitosterol (l.a.). Glycerol (r.). |
11550 Remain from interior | Inorganics a: Silicates, SiO2; calcium oxalate (whewhellite), copper oxalate (moolooite) (r.). Organics b: carboxylic acids, metal soaps, esters. | Methanol: glyceryl mono- and diesters, fatty monoacids, diacids, and carboxylates (metal soaps). Acetone: acylglycerols, fatty monoacids (r.). Dichloromethane: acylglycerols (l.a.), short/mid-chain fatty monoacids (r.). | FAs: C16:0 (r.) and C18:0; diacids C8di, C9di (r.) and C13di. Even-numbered sat. FAs: C8:0–C26:0. Odd-numbered sat. FAs: C9:0 and C15:0. Unsat. FAs: C18:1. Full range of diacids: C4di–C14di. Glycerol (l.a.), MAG C16-G and C18-G; glyceric acid (tr). |
11551 Remain from interior | Inorganics a: Silicates, SiO2, copper oxalate (moolooite). Organics b: carboxylic acids, metal soaps, esters. | Methanol: Glycerol and/or acylglycerols (r.), fatty acids (r.), diacids, carboxylates (metal soaps). Acetone: acylglycerols (r.), fatty monoacids (r.), diacids, anhydrides/lactones (l.a.). Dichloromethane: acylglycerols (r.), short/mid-chain fatty monoacids (r.). | C16:0 (r.), C18:0, C22:0 and C24:0 FAs; diacids C8di (r.), C9di and C13di. Even-numbered sat. FAs (l.a.): C8:0–C28:0 Odd-numbered sat. FA: C9:0 Glycerol (l.a.), C16- and C18-MAG; glyceric acid (tr). HCs: sat. C43–C49 and unsat. C28–C31. [meaning?] |
11573 Remain from connection area | Inorganics a: calcite, silicates, calcium oxalate (whewhellite) (r.) Organics b: carboxylic acids (l.a.), esters (l.a.). | Methanol: acylglycerols, carboxylates (metal soaps). Acetone: acylglycerols, fatty monoacids (r.). Dichloromethane: acylglycerols, short/mid-chain fatty monoacids. | Diacids C8di, C9di (r.), C11di and C13di (r.). Glycerol (r.). Even-numbered sat. FAs C8:0–C24:0. Odd-numbered sat. FA: C9:0 MAG C16-G and C18-G. Diacids: C4di–C15di. |
11596 Remain from interior | Inorganics a: calcium oxalate (whewhellite) (r.) Organics: carboxylic acids (l.a.), esters (l.a.). | Methanol: Glycerol, carboxylates (metal soaps). Acetone: unspecified trace amounts. Dichloromethane: short/mid-chain fatty monoacids (l.a.). | Diacids C8di and C9di (r.). Glycerol and MAG C16-G and C18-G. Even-numbered sat. FAs C8:0–C24:0. Odd-numbered sat. FA: C9:0 MAG C16-G and C18-G. Diacids: C4di–C14di. HCs: sat. C23, C24, C27, C30. |
11598 Remain from interior | Inorganics a: calcite (l.a.), silicates (r), oxalates. Organics b: carboxylic acids, carboxylate salts (tr.), esters. | Methanol: acylglycerols, fatty acids, carboxylates (metal soaps). Acetone: acylglycerols. Dichloromethane: short/mid-chain acylglycerols (r.), fatty monoacids (tr.). | Diacids C8di and C9di (r.). Glycerol and MAG C16-G and C18-G. Even-numbered sat. FAs C8:0–C24:0. Odd-numbered sat. FA: C9:0 and C17:0 unsat. FAs: C18:1. MAG C16-G and C18-G. Diacids: C4di–C14di. HCs: sat. C23, C24, C27, C30. Hypoxanthine, maltose (possible contaminants). |
11622A Remain from cavities in connection area | Inorganics a: silicates (l.a.), calcium oxalate (whewhellite) (r.) Organics b: carboxylic acids (l.a.), carboxylate salts (tr.), esters. | Methanol: acylglycerols, carboxylates (metal soaps). Acetone: acylglycerols. Dichloromethane: acylglycerols, short/mid-chain fatty monoacids. | Dihydroxy FA: 13,14-dihydroxy C22:0 FA (r.); Diacids C8di, C9di (r.) and C11di (r.); Glycerol (r.). Even-numbered sat. FAs C8:0–C24:0. Odd-numbered sat. FA: C9:0 MAG: C16-G and C18-G Diacids: C4di–C15di. Dehydroabietic acid and 7-oxo-dehydroabietic acid. |
11622B Powder from addition on vessel body | Inorganics a: Gypsum (r.), calcite, silicates, SiO2 (r). Organics b: n.d. | No organics found. | n.a. |
11633A Remain from connection area | Inorganics a: Silicates, SiO2, (r), calcium oxalate (whewhellite) (r.), copper oxalate (moolooite) (tr.). Organics b: carboxylic acids (l.a.), metal soaps (r.), esters (l.a.). | Methanol: acylglycerols, carboxylates (metal soaps). Acetone: acylglycerols. Dichloromethane: acylglycerols, short/mid-chain fatty monoacids (r.). | Glycerol (r.); C22(diOH) (r.). Even-numbered sat. FAs C8:0–C24:0. Odd-numbered sat. FA: C9:0 and C17:0. MAG: C16-G and C18-G. Diacids: C4di–C15di. |
11633B Powder from interior remains | Inorganics a: Gypsum (r.), calcite, silicates, SiO2. Organics: n.d. | No organics found. | n.a. |
Maximum, Wavenumber (cm−1) | Assignment 1 | Type(s) of Compounds |
---|---|---|
3700–3696 | vOH | Hydroxides or crystalline water in silicates (clay) |
3624–3620 | vOH | Hydroxides or crystalline water in silicates (clay) |
3440–3400 (br) | vOH | Hydroxyl in acylglycerols, hydroxy-acids Adsorbed water in silicates |
3300–3200 | vOH | Carboxyl in free FA |
2960–2950 | vasCH3 | FA and FAE |
2951–2937 | vasCH2 | Diacids |
2940–2935 | C4–C6 | |
2930–2920 | C7–C12 | |
2918–2910 | C13–C18 | |
1740–1730 | vC=O | Fatty esters (acylglycerols) |
1718–1712 | Short-chain fatty monoacids (C4–C9) | |
1711–1709 | Mid-chain fatty monoacids (C10–C12) | |
1708–1701 | Long-chain fatty monoacids (>C12) | |
1700–1695 | Diacids | |
1650–1630 (br) | δOH | Adsorbed water in silicates |
1640 | vasCOO- | Copper oxalate (moolooite) |
1623 | vasCOO- | Calcium oxalate (whewhellite) |
1590 1551 1541 | vasCOO- | Fatty acid metal salts |
1470 | δCH2 | Alkyl chains in diacids and fatty esters (acylglycerols) |
1458 | δCH2 | Alkyl chains in monocarboxylic acids |
1425 | δipC–O–H | Diacids |
1412 | δCH2 | Alkyl chains in diacids |
1414–1408 | δipC–O–H | Fatty monoacids |
1393 | δipC–O–H | Alcohol in glycerol or glyceryl group |
1380–1364 | δsCH3 | Terminal methyl groups in fatty monoacids and their glycerol esters; relatively stronger as compared to δCH2 in short-chain monoacids |
1317 | vsCOO- | Calcium oxalate (whewhellite) Copper oxalate (moolooite) |
1180 | vC–O–C=O | Ester links (acylglycerols) |
1105 | vC–O–C=O | Ester links (acylglycerols) |
1090 | vSi–O | Silicates: quartz sand |
1026 | vSi–O | Silicates: clay |
vC–O–H | Glycerol or glyceryl group | |
817 | δOCO | In carboxylates: copper oxalate (moolooite) |
780 | δOCO | In carboxylates: calcium oxalate (whewhellite) |
798/779 | vasSi–O–Si | Silicates: quartz sand |
722, 691 | ρCH2 | Long alkyl chain of fatty acids and salts |
527 | δOSiO | Silicates |
467 | δOSiO | Silicates |
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Koupadi, K.; Boyatzis, S.C.; Roumpou, M.; Kalogeropoulos, N.; Kotzamani, D. Organic Remains in Early Christian Egyptian Metal Vessels: Investigation with Fourier Transform Infrared Spectroscopy and Gas Chromatography–Mass Spectrometry. Heritage 2021, 4, 3611-3629. https://doi.org/10.3390/heritage4040199
Koupadi K, Boyatzis SC, Roumpou M, Kalogeropoulos N, Kotzamani D. Organic Remains in Early Christian Egyptian Metal Vessels: Investigation with Fourier Transform Infrared Spectroscopy and Gas Chromatography–Mass Spectrometry. Heritage. 2021; 4(4):3611-3629. https://doi.org/10.3390/heritage4040199
Chicago/Turabian StyleKoupadi, Kyriaki, Stamatis C. Boyatzis, Maria Roumpou, Nick Kalogeropoulos, and Despoina Kotzamani. 2021. "Organic Remains in Early Christian Egyptian Metal Vessels: Investigation with Fourier Transform Infrared Spectroscopy and Gas Chromatography–Mass Spectrometry" Heritage 4, no. 4: 3611-3629. https://doi.org/10.3390/heritage4040199