Gas Chromatography Coupled to High Resolution Time-of-Flight Mass Spectrometry as a High-Throughput Tool for Characterizing Geochemical Biomarkers in Sediments
The performance of gas chromatography coupled to high-resolution time-of-flight mass spectrometry (GC-HRTofMS) for characterizing geochemical biomarkers from sediment samples was evaluated. Two approaches to obtain the geochemical biomarkers were tested: (1) extraction with organic solvent and subse...
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| Format: | Article |
| Language: | English |
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Wiley
2018-01-01
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| Series: | International Journal of Analytical Chemistry |
| Online Access: | http://dx.doi.org/10.1155/2018/2560498 |
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| author | Hector Henrique Ferreira Koolen Clécio Fernando Klitzke Joe Binkley Jeffrey Patrick Ana Cecília Rizatti de Albergaria-Barbosa Rolf Roland Weber Márcia Caruso Bícego Marcos Nogueira Eberlin Giovana Anceski Bataglion |
| author_facet | Hector Henrique Ferreira Koolen Clécio Fernando Klitzke Joe Binkley Jeffrey Patrick Ana Cecília Rizatti de Albergaria-Barbosa Rolf Roland Weber Márcia Caruso Bícego Marcos Nogueira Eberlin Giovana Anceski Bataglion |
| author_sort | Hector Henrique Ferreira Koolen |
| collection | DOAJ |
| description | The performance of gas chromatography coupled to high-resolution time-of-flight mass spectrometry (GC-HRTofMS) for characterizing geochemical biomarkers from sediment samples was evaluated. Two approaches to obtain the geochemical biomarkers were tested: (1) extraction with organic solvent and subsequent derivatization and (2) in-situ derivatization thermal desorption. Results demonstrated that both approaches can be conveniently applied for simultaneous characterization of many geochemical biomarkers (alkanes, alkanols, sterols, and fatty acids), avoiding conventional time-consuming purification procedures. GC-HRTofMS reduces both sample preparation time and the number of chromatographic runs compared to traditional methodologies used in organic geochemistry. Particularly, the approach based on in-situ derivatization thermal desorption represents a very simple method that can be performed in-line employing few milligrams of sediment, eliminating the need for any sample preparation and solvent use. The high resolving power (m/Δm50% 25,000) and high mass accuracy (error ≤ 1 ppm) offered by the “zig-zag” time-of-flight analyzer were indispensable to resolve the complexity of the total ion chromatograms, representing a high-throughput tool. Extracted ion chromatograms using exact m/z were useful to eliminate many isobaric interferences and to increase significantly the signal to noise ratio. Characteristic fragment ions allowed the identification of homologous series, such as alkanes, alkanols, fatty acids, and sterols. Polycyclic aromatic hydrocarbons were also identified in the samples by their molecular ions. The characterization of geochemical biomarkers along a sedimentary core collected in the area of Valo Grande Channel (Cananéia-Iguape Estuarine-Lagunar System (São Paulo, Brazil)) provided evidences of environmental changes. Sediments deposited before opening of channel showed dominance of biomarkers from mangrove vegetation, whereas sediments of the pos-opening period showed an increase of biomarkers from aquatic macrophyte (an invasive vegetation). |
| format | Article |
| id | doaj-art-54cdfbb1493d462dae156835b819377d |
| institution | Kabale University |
| issn | 1687-8760 1687-8779 |
| language | English |
| publishDate | 2018-01-01 |
| publisher | Wiley |
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| series | International Journal of Analytical Chemistry |
| spelling | doaj-art-54cdfbb1493d462dae156835b819377d2025-02-03T05:43:32ZengWileyInternational Journal of Analytical Chemistry1687-87601687-87792018-01-01201810.1155/2018/25604982560498Gas Chromatography Coupled to High Resolution Time-of-Flight Mass Spectrometry as a High-Throughput Tool for Characterizing Geochemical Biomarkers in SedimentsHector Henrique Ferreira Koolen0Clécio Fernando Klitzke1Joe Binkley2Jeffrey Patrick3Ana Cecília Rizatti de Albergaria-Barbosa4Rolf Roland Weber5Márcia Caruso Bícego6Marcos Nogueira Eberlin7Giovana Anceski Bataglion8ThoMSon Mass Spectrometry Laboratory, Institute of Chemistry, University of Campinas (UNICAMP), 13083-970, Campinas, SP, BrazilLECO Corporation, 49085, St. Joseph, MI, USALECO Corporation, 49085, St. Joseph, MI, USALECO Corporation, 49085, St. Joseph, MI, USALaboratory of Marine Geochemistry, Geoscience Institute, Federal University of Bahia (UFBA), 40170-020, Salvador, BA, BrazilMarine Organic Chemistry Laboratory, Oceanographic Institute, University of São Paulo (USP), 05508-120, São Paulo, SP, BrazilMarine Organic Chemistry Laboratory, Oceanographic Institute, University of São Paulo (USP), 05508-120, São Paulo, SP, BrazilThoMSon Mass Spectrometry Laboratory, Institute of Chemistry, University of Campinas (UNICAMP), 13083-970, Campinas, SP, BrazilThoMSon Mass Spectrometry Laboratory, Institute of Chemistry, University of Campinas (UNICAMP), 13083-970, Campinas, SP, BrazilThe performance of gas chromatography coupled to high-resolution time-of-flight mass spectrometry (GC-HRTofMS) for characterizing geochemical biomarkers from sediment samples was evaluated. Two approaches to obtain the geochemical biomarkers were tested: (1) extraction with organic solvent and subsequent derivatization and (2) in-situ derivatization thermal desorption. Results demonstrated that both approaches can be conveniently applied for simultaneous characterization of many geochemical biomarkers (alkanes, alkanols, sterols, and fatty acids), avoiding conventional time-consuming purification procedures. GC-HRTofMS reduces both sample preparation time and the number of chromatographic runs compared to traditional methodologies used in organic geochemistry. Particularly, the approach based on in-situ derivatization thermal desorption represents a very simple method that can be performed in-line employing few milligrams of sediment, eliminating the need for any sample preparation and solvent use. The high resolving power (m/Δm50% 25,000) and high mass accuracy (error ≤ 1 ppm) offered by the “zig-zag” time-of-flight analyzer were indispensable to resolve the complexity of the total ion chromatograms, representing a high-throughput tool. Extracted ion chromatograms using exact m/z were useful to eliminate many isobaric interferences and to increase significantly the signal to noise ratio. Characteristic fragment ions allowed the identification of homologous series, such as alkanes, alkanols, fatty acids, and sterols. Polycyclic aromatic hydrocarbons were also identified in the samples by their molecular ions. The characterization of geochemical biomarkers along a sedimentary core collected in the area of Valo Grande Channel (Cananéia-Iguape Estuarine-Lagunar System (São Paulo, Brazil)) provided evidences of environmental changes. Sediments deposited before opening of channel showed dominance of biomarkers from mangrove vegetation, whereas sediments of the pos-opening period showed an increase of biomarkers from aquatic macrophyte (an invasive vegetation).http://dx.doi.org/10.1155/2018/2560498 |
| spellingShingle | Hector Henrique Ferreira Koolen Clécio Fernando Klitzke Joe Binkley Jeffrey Patrick Ana Cecília Rizatti de Albergaria-Barbosa Rolf Roland Weber Márcia Caruso Bícego Marcos Nogueira Eberlin Giovana Anceski Bataglion Gas Chromatography Coupled to High Resolution Time-of-Flight Mass Spectrometry as a High-Throughput Tool for Characterizing Geochemical Biomarkers in Sediments International Journal of Analytical Chemistry |
| title | Gas Chromatography Coupled to High Resolution Time-of-Flight Mass Spectrometry as a High-Throughput Tool for Characterizing Geochemical Biomarkers in Sediments |
| title_full | Gas Chromatography Coupled to High Resolution Time-of-Flight Mass Spectrometry as a High-Throughput Tool for Characterizing Geochemical Biomarkers in Sediments |
| title_fullStr | Gas Chromatography Coupled to High Resolution Time-of-Flight Mass Spectrometry as a High-Throughput Tool for Characterizing Geochemical Biomarkers in Sediments |
| title_full_unstemmed | Gas Chromatography Coupled to High Resolution Time-of-Flight Mass Spectrometry as a High-Throughput Tool for Characterizing Geochemical Biomarkers in Sediments |
| title_short | Gas Chromatography Coupled to High Resolution Time-of-Flight Mass Spectrometry as a High-Throughput Tool for Characterizing Geochemical Biomarkers in Sediments |
| title_sort | gas chromatography coupled to high resolution time of flight mass spectrometry as a high throughput tool for characterizing geochemical biomarkers in sediments |
| url | http://dx.doi.org/10.1155/2018/2560498 |
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