Characterization of Severely Biodegraded Crude Oils Using Negative-Ion ESI Orbitrap MS, GC-NCD and GC-SCD: Insights into Heteroatomic Compounds Biodegradation
A slightly and two severely biodegraded crude oils with the same origin were analysed using negative-ion electrospray ionization Orbitrap mass spectrometry (ESI Orbitrap MS), gas chromatography-nitrogen chemiluminescence detector (GC-NCD), and GC-sulfur chemiluminescence detector (GC-SCD) to investi...
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MDPI AG
2021-01-01
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| Series: | Energies |
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| Online Access: | https://www.mdpi.com/1996-1073/14/2/300 |
| _version_ | 1797415282006818816 |
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| author | Xiong Cheng Dujie Hou |
| author_facet | Xiong Cheng Dujie Hou |
| author_sort | Xiong Cheng |
| collection | DOAJ |
| description | A slightly and two severely biodegraded crude oils with the same origin were analysed using negative-ion electrospray ionization Orbitrap mass spectrometry (ESI Orbitrap MS), gas chromatography-nitrogen chemiluminescence detector (GC-NCD), and GC-sulfur chemiluminescence detector (GC-SCD) to investigate the composition of heteroatomic compounds and their fate during severe biodegradation and to provide insights into biodegradation pathway of hopanes, nitrogen- and sulfur-containing compounds. Twelve heteroatomic compound classes, including O<sub>1</sub>–O<sub>5</sub>, N<sub>1</sub>, N<sub>2</sub>, N<sub>1</sub>O<sub>1</sub>–N<sub>1</sub>O<sub>3</sub>, N<sub>1</sub>S<sub>1</sub> and O<sub>3</sub>S<sub>1</sub>, were detected and assigned unambiguous molecular formulae. The O<sub>1</sub> species are likely phenols with additional naphthenic and/or aromatic rings. Carboxylic acids (O<sub>2</sub> species) are originated from oxidation of hydrocarbons, and the tricyclic naphthenic acids are the most resistant, followed by bicyclics. Hopanes could be biodegraded by demethylation or by unstable hopanoic acids as intermediates to yield 25-norhopanes. The N<sub>1</sub> species are pyrrolic compounds with naphthenic and/or aromatic rings and are dominated by carbazole analogues. Carbazoles with more aromatic rings are more resistant to biodegradation. The N<sub>1</sub> species could be converted to N<sub>1</sub>O<sub>1</sub> and N<sub>1</sub>O<sub>2</sub> compounds via ring-opening and hydroxylation pathways. The N<sub>1</sub>S<sub>1</sub> species contain a pyrrolic and cyclic sulfide structure, which are highly recalcitrant to biodegradation. Benzothiophenes and dibenzothiophenes might be biodegraded via the complete pathway or the sulfur-specific pathway rather than by other pathways to yield acidic oxygenated sulfur compounds. |
| first_indexed | 2024-03-09T05:46:32Z |
| format | Article |
| id | doaj.art-cc7386518e524f6fbdb210cafab3cda4 |
| institution | Directory Open Access Journal |
| issn | 1996-1073 |
| language | English |
| last_indexed | 2024-03-09T05:46:32Z |
| publishDate | 2021-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Energies |
| spelling | doaj.art-cc7386518e524f6fbdb210cafab3cda42023-12-03T12:21:05ZengMDPI AGEnergies1996-10732021-01-0114230010.3390/en14020300Characterization of Severely Biodegraded Crude Oils Using Negative-Ion ESI Orbitrap MS, GC-NCD and GC-SCD: Insights into Heteroatomic Compounds BiodegradationXiong Cheng0Dujie Hou1School of Energy Resources, China University of Geosciences, Beijing 100083, ChinaSchool of Energy Resources, China University of Geosciences, Beijing 100083, ChinaA slightly and two severely biodegraded crude oils with the same origin were analysed using negative-ion electrospray ionization Orbitrap mass spectrometry (ESI Orbitrap MS), gas chromatography-nitrogen chemiluminescence detector (GC-NCD), and GC-sulfur chemiluminescence detector (GC-SCD) to investigate the composition of heteroatomic compounds and their fate during severe biodegradation and to provide insights into biodegradation pathway of hopanes, nitrogen- and sulfur-containing compounds. Twelve heteroatomic compound classes, including O<sub>1</sub>–O<sub>5</sub>, N<sub>1</sub>, N<sub>2</sub>, N<sub>1</sub>O<sub>1</sub>–N<sub>1</sub>O<sub>3</sub>, N<sub>1</sub>S<sub>1</sub> and O<sub>3</sub>S<sub>1</sub>, were detected and assigned unambiguous molecular formulae. The O<sub>1</sub> species are likely phenols with additional naphthenic and/or aromatic rings. Carboxylic acids (O<sub>2</sub> species) are originated from oxidation of hydrocarbons, and the tricyclic naphthenic acids are the most resistant, followed by bicyclics. Hopanes could be biodegraded by demethylation or by unstable hopanoic acids as intermediates to yield 25-norhopanes. The N<sub>1</sub> species are pyrrolic compounds with naphthenic and/or aromatic rings and are dominated by carbazole analogues. Carbazoles with more aromatic rings are more resistant to biodegradation. The N<sub>1</sub> species could be converted to N<sub>1</sub>O<sub>1</sub> and N<sub>1</sub>O<sub>2</sub> compounds via ring-opening and hydroxylation pathways. The N<sub>1</sub>S<sub>1</sub> species contain a pyrrolic and cyclic sulfide structure, which are highly recalcitrant to biodegradation. Benzothiophenes and dibenzothiophenes might be biodegraded via the complete pathway or the sulfur-specific pathway rather than by other pathways to yield acidic oxygenated sulfur compounds.https://www.mdpi.com/1996-1073/14/2/300biodegradationcrude oilultra-high-resolution mass spectrometryESI Orbitrap MSNSO compounds |
| spellingShingle | Xiong Cheng Dujie Hou Characterization of Severely Biodegraded Crude Oils Using Negative-Ion ESI Orbitrap MS, GC-NCD and GC-SCD: Insights into Heteroatomic Compounds Biodegradation Energies biodegradation crude oil ultra-high-resolution mass spectrometry ESI Orbitrap MS NSO compounds |
| title | Characterization of Severely Biodegraded Crude Oils Using Negative-Ion ESI Orbitrap MS, GC-NCD and GC-SCD: Insights into Heteroatomic Compounds Biodegradation |
| title_full | Characterization of Severely Biodegraded Crude Oils Using Negative-Ion ESI Orbitrap MS, GC-NCD and GC-SCD: Insights into Heteroatomic Compounds Biodegradation |
| title_fullStr | Characterization of Severely Biodegraded Crude Oils Using Negative-Ion ESI Orbitrap MS, GC-NCD and GC-SCD: Insights into Heteroatomic Compounds Biodegradation |
| title_full_unstemmed | Characterization of Severely Biodegraded Crude Oils Using Negative-Ion ESI Orbitrap MS, GC-NCD and GC-SCD: Insights into Heteroatomic Compounds Biodegradation |
| title_short | Characterization of Severely Biodegraded Crude Oils Using Negative-Ion ESI Orbitrap MS, GC-NCD and GC-SCD: Insights into Heteroatomic Compounds Biodegradation |
| title_sort | characterization of severely biodegraded crude oils using negative ion esi orbitrap ms gc ncd and gc scd insights into heteroatomic compounds biodegradation |
| topic | biodegradation crude oil ultra-high-resolution mass spectrometry ESI Orbitrap MS NSO compounds |
| url | https://www.mdpi.com/1996-1073/14/2/300 |
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