Elucidation of the macromolecular composition of fossil biopolymers using Py-GC×GC-TOFMS

Umamaheswaran, Raman; Dutta, Suryendu; Kumar, Sumit

doi:10.1016/j.orggeochem.2020.104139

Cited by 11 publications

(8 citation statements)

References 29 publications

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“…20,21,69 The specificity provided by this technique even using minute amounts of sample material is an important advantage when analyzing fossil material. Umamaheswaran et al 26 reported an increased sensitivity and resolution capacity of Py-GC × GC-TOFMS as compared to Py-GC−MS, in an analysis involving G. prisca, Tasmanites, and fossil resin. Bidimensional analysis was able to resolve more complex compounds that were present in very low abundances using only a small amount of sample material.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…17−19 However, in recent years, two-dimensional gas chromatography has been shown to generate higher resolution chromatographic peaks than single dimension 20 and has been previously established as a method for biomarker analysis of lipids. 21−24 Hence, we opt for Py-GC × GC-TOFMS due to its increased sensitivity, resolution power, and ability to detect complex compounds in low abundances, even in fossil materials, 25,26 and show the preservation of chitin in Pliocene fungi based on specific diagnostic markers as an example for the potential further extension of this technique in the detection of chitin in fossils from deep time.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The primary column was an Rxi-5Sil MS (5% phenylsiloxane−95% methylsiloxane; 30 m × 0.25 mm × 0.25 μm), while the secondary column was an Rxi-17Sil MS (50% phenyl−50% methylpolysiloxane; 1.05 m × 0.25 mm × 0.25 μm). The GC × GC method was carried out as per the procedure reported by Dutta et al 25 and Umamaheswaran et al 26 The primary oven temperature was kept isothermal at 50 °C for 2 min, increased to 180 °C at a rate of 10 °C min −1 , subsequently increased to 270 °C at 5 °C min −1 , finally increased to 295 °C at a rate of 3 °C min −1 , and kept isothermal for 10 min. The secondary oven was kept at an offset temperature of +10 °C with respect to the primary oven temperature, and the modulator was kept at an offset of +15 °C with respect to the same.…”

Section: ■ Introductionmentioning

confidence: 99%

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Identification of Chitin in Pliocene Fungi Using Py-GC × GC-TOFMS: Potential Implications for the Study of the Evolution of the Fungal Clade in Deep Time

et al. 2022

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Molecular dating estimates the origin of the fungal clade to the Pre-Cambrian. Yet, the oldest unambiguous fungal fossils date to the Ordovician and show remarkable diversity and organizational development. Recent studies have suggested that the dates for the emergence of fungi in the fossil record may be pushed back to the Proterozoic. However, the nonspecificity of the methods used in those studies necessitates the employment of a wider variety of analytical techniques that can independently verify the presence of chitin, a crucial prerequisite in the assignment of fungal affinity, particularly of putative fossils from the Pre-Cambrian. In this paper, we propose Py-GC × GC-TOFMS as an example of one such technique. We analyze fungal fossils from the Pliocene. We find that a suite of N-bearing compounds are present in the pyrolysis products of these fossils, from which we suggest that 3-acetamidopyrones and their methylated homologues can serve as specific pyrolytic markers for chitin. We discuss both how this technique can potentially be used to differentiate between biopolymers, including those similar to chitin such as peptidoglycan, and the potential implications of identifying such markers in fossils from deep time. We conclude that Py-GC × GC-TOFMS is a promising technique that can potentially be used alongside, or independent of, staining methods to detect the presence of chitin in fossils.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Identification of Chitin in Pliocene Fungi Using Py-GC × GC-TOFMS: Potential Implications for the Study of the Evolution of the Fungal Clade in Deep Time

et al. 2022

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“…Fossil resins of various ages are found in many places around the world. The number of publications on these speci c bituminous substances originated from the caustobiolite group is constantly increasing in every year [1][2][3][4][5][6][7][8][9][10][11][12][13] . Over a hundred of different fossil resins have been described, so far 14 .…”

Section: Introductionmentioning

confidence: 99%

The Characteristics and Origin of Amber Deposits in the Dominican Republic

Stach

Natkaniec‐Nowak

Dumańska-Słowik

et al. 2021

Preprint

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Mineralogical and geochemical characteristics of amber deposits located in the Dominican Republic, i.e., Hato Mayor Province of the Eastern Mining District (EMD) in the Cordillera Oriental, and Santiago Province of the Northern Mining District (NMD) in the Cordillera Septentrional were performed. The results of analyses of amber-bearing sediments collected from the borehole in Siete Cañadas area (EMD) were referenced to the petrological data obtained for the coaly shales from La Cumbre (NMD). The mineralogy of the rocks was described using transmitted and reflected light microscopy, scanning electron microscopy, Powder X-ray diffraction and Fourier Transform Raman Spectroscopy. Biomarker analyses by the gas chromatography-mass spectrometry were used to trace the genetic source and transformation stage of abundant organic matter hosted in the core sediments. Our findings indicated that basins in EMD and NMD regions were different isolated palaeosettings, in which under the influence of local physicochemical factors the terrigenous material was transformed and got maturated. In both amber deposits, the sedimentation of clastic and organic material proceeded in the presence of marine conditions. In case of the NMD area, the sedimentation underwent probably in the conditions of the lagoon environment, a shallow maritime lake or periodically flooded plain, that facilitated organic matter decomposition and carbonation from meta-lignite to sub-bituminous coal (random reflectance of coal - Rro = 0,39%). In the EMD region, the sedimentation took place in a deeper basin, where terrigenous material was likely mixed with material found in situ (fauna fossils, carbonate-group minerals) to form the mudstones enriched in bituminous substance of low maturity. The organic matter found in the rocks from both regions is of mixed terrestrial/marine origin and was deposited in the presence of low oxygen concentration and reducing and/or dysoxic conditions.

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“…Fossil resins of various ages are found in many places around the world. The number of publications on these specific bituminous substances originated from the caustobiolite group is constantly increasing in every year 1 – 13 . Over a hundred of different fossil resins have been described, so far 14 .…”

Section: Introductionmentioning

confidence: 99%

The study of Dominican amber-bearing sediments from Siete Cañadas and La Cumbre with a discussion on their origin

Stach

Natkaniec‐Nowak

Dumańska-Słowik

et al. 2021

Sci Rep

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The paper presents comprehensive mineralogical and geochemical characteristics of Dominican amber-bearing sediments from Siete Cañadas, Hato Mayor Province of the Eastern Mining District (EMD) in the Cordillera Oriental. The characteristics of rocks collected from the borehole in Siete Cañadas area (EMD) were compared with petrography of coaly shales from La Cumbre in the Northern Mining District (NMD). The mineralogy of the rocks was determined using transmitted and reflected light microscopy, scanning electron microscopy, Powder X-ray diffraction and Fourier Transform Raman Spectroscopy. Biomarker analyses by the gas chromatography–mass spectrometry were used to trace the genetic source and transformation stage of organic matter hosted in the core sediments. In this study, the characteristics of rocks from La Cumbre were supplemented with the petrographic data from our studies reported earlier. Based on the findings, it has been concluded that the basins in the investigated parts of the EMD and NMD regions were likely characterized by different, isolated palaeosettings. Transformation and maturation of terrigenous material were affected by locally occurring physicochemical conditions. In both amber deposits, the sedimentation of clastic and organic material proceeded in the presence of marine conditions. In case of the La Cumbre deposit (NMD area), the sedimentation underwent probably in the conditions of the lagoon environment, a shallow maritime lake or periodically flooded plain that facilitated organic matter decomposition and carbonation from meta-lignite to sub-bituminous coal (random reflectance of coal—Rro = 0.39%). In the Siete Cañadas (EMD region), the sedimentation took place in a shallow saltwater basin, where terrigenous material was likely mixed with material found in situ (fauna fossils, carbonate-group minerals) to form the mudstones enriched in bituminous substance of low maturity. The organic matter found in the rocks from both deposits is of mixed terrestrial/marine origin and was deposited in the presence of low oxygen concentration and reducing and/or dysoxic conditions.

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Elucidation of the macromolecular composition of fossil biopolymers using Py-GC×GC-TOFMS

Cited by 11 publications

References 29 publications

Identification of Chitin in Pliocene Fungi Using Py-GC × GC-TOFMS: Potential Implications for the Study of the Evolution of the Fungal Clade in Deep Time

Identification of Chitin in Pliocene Fungi Using Py-GC × GC-TOFMS: Potential Implications for the Study of the Evolution of the Fungal Clade in Deep Time

The Characteristics and Origin of Amber Deposits in the Dominican Republic

The study of Dominican amber-bearing sediments from Siete Cañadas and La Cumbre with a discussion on their origin

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