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Archaeal and bacterial glycerol dialkyl glycerol tetraether (GDGT) lipids in environmental samples by high temperature-gas chromatography with flame ionisation and time-of-flight mass spectrometry detection

Archaeal and bacterial glycerol dialkyl glycerol tetraether (GDGT) lipids in environmental samples by high temperature-gas chromatography with flame ionisation and time-of-flight mass spectrometry detection
Archaeal and bacterial glycerol dialkyl glycerol tetraether (GDGT) lipids in environmental samples by high temperature-gas chromatography with flame ionisation and time-of-flight mass spectrometry detection
Archaeal isoprenoidal glycerol dibiphytanyl glycerol tetraether lipids (iGDGTs) and their non-isoprenoidal branched bacterial analogues (brGDGTs) have widespread applications in biogeochemistry and paleothermometry. Analysis of GDGTs usually involves separation using high performance liquid chromatography, typically coupled via atmospheric pressure chemical ionisation to mass spectrometric detection in selected ion-monitoring mode (HPLC–APCI-MS). However, reliable determination of ratios and, in particular, quantification by this technique, can be challenging due to differences in ionisation efficiencies of the various compounds. Quantification of GDGTs also relies on external calibration of the relative response to an internal standard with authenticated GDGTs, which are often not readily accessible. Here, we tested the suitability of high temperature gas chromatography with flame ionisation detection (HTGC-FID) for the determination of concentrations and tetraether lipid-based ratios in marine and terrestrial samples. For this, we identified GDGTs in environmental samples using HTGC coupled to time-of-flight mass spectrometry (HTGC–MS). Using a purified GDGT standard, we show we can quantify GDGT-0 in environmental samples by GC-FID. Some GDGT-based ratios measured by HTGC-FID exhibited a linear correlation (1:1) with ratios derived from HPLC–MS and weight-based ratios of mixtures of purified standards. However, ratios relying on minor isomers, such as TEX86 and MBT/CBT have many unresolved challenges for determination by HTGC. Detection limits were higher than for HPLC–MS. However, the advantages of employing HTGC-based methods include: (1) the independence from MS tuning-related differences in ionisation energies; (2) the potential for direct comparison with other, non-GDGT based biomarkers; and (3) a more complete insight into biomarker distributions in environmental samples by the extension of the temperature range. Quantitative elution of GDGTs from a HTGC column as demonstrated herein, will also enable their analysis by compound-specific isotope ratio mass spectrometry.
0146-6380
10-21
Lengger, Sabine K.
93ef3c82-6526-427d-a10a-935dbc559d03
Sutton, Paul A.
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Rowland, Steven J.
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Hurley, Sarah J.
c976020b-13ed-443e-b9a6-fd0cec88c4fa
Pearson, Ann
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Naafs, B. David A.
b4e4a3c0-ef86-476f-a439-3ce7e192337a
Dang, Xinyue
ca6d23e1-a539-44b3-b81b-b99a236978a2
Inglis, Gordon N.
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Pancost, Richard D.
5914e19e-7777-4304-9fd8-86e2e9cfe8a1
Lengger, Sabine K.
93ef3c82-6526-427d-a10a-935dbc559d03
Sutton, Paul A.
b9a9d1cf-1a82-4054-a47f-6be9674b9c75
Rowland, Steven J.
1f11586f-fda1-4e78-9c78-febdea0dc81c
Hurley, Sarah J.
c976020b-13ed-443e-b9a6-fd0cec88c4fa
Pearson, Ann
2bda704d-0e4b-4008-8329-6c99c699aedb
Naafs, B. David A.
b4e4a3c0-ef86-476f-a439-3ce7e192337a
Dang, Xinyue
ca6d23e1-a539-44b3-b81b-b99a236978a2
Inglis, Gordon N.
1651196d-916c-43cb-b5a0-9b3ecaf5d664
Pancost, Richard D.
5914e19e-7777-4304-9fd8-86e2e9cfe8a1

Lengger, Sabine K., Sutton, Paul A., Rowland, Steven J., Hurley, Sarah J., Pearson, Ann, Naafs, B. David A., Dang, Xinyue, Inglis, Gordon N. and Pancost, Richard D. (2018) Archaeal and bacterial glycerol dialkyl glycerol tetraether (GDGT) lipids in environmental samples by high temperature-gas chromatography with flame ionisation and time-of-flight mass spectrometry detection. Organic Geochemistry, 121, 10-21. (doi:10.1016/j.orggeochem.2018.03.012).

Record type: Article

Abstract

Archaeal isoprenoidal glycerol dibiphytanyl glycerol tetraether lipids (iGDGTs) and their non-isoprenoidal branched bacterial analogues (brGDGTs) have widespread applications in biogeochemistry and paleothermometry. Analysis of GDGTs usually involves separation using high performance liquid chromatography, typically coupled via atmospheric pressure chemical ionisation to mass spectrometric detection in selected ion-monitoring mode (HPLC–APCI-MS). However, reliable determination of ratios and, in particular, quantification by this technique, can be challenging due to differences in ionisation efficiencies of the various compounds. Quantification of GDGTs also relies on external calibration of the relative response to an internal standard with authenticated GDGTs, which are often not readily accessible. Here, we tested the suitability of high temperature gas chromatography with flame ionisation detection (HTGC-FID) for the determination of concentrations and tetraether lipid-based ratios in marine and terrestrial samples. For this, we identified GDGTs in environmental samples using HTGC coupled to time-of-flight mass spectrometry (HTGC–MS). Using a purified GDGT standard, we show we can quantify GDGT-0 in environmental samples by GC-FID. Some GDGT-based ratios measured by HTGC-FID exhibited a linear correlation (1:1) with ratios derived from HPLC–MS and weight-based ratios of mixtures of purified standards. However, ratios relying on minor isomers, such as TEX86 and MBT/CBT have many unresolved challenges for determination by HTGC. Detection limits were higher than for HPLC–MS. However, the advantages of employing HTGC-based methods include: (1) the independence from MS tuning-related differences in ionisation energies; (2) the potential for direct comparison with other, non-GDGT based biomarkers; and (3) a more complete insight into biomarker distributions in environmental samples by the extension of the temperature range. Quantitative elution of GDGTs from a HTGC column as demonstrated herein, will also enable their analysis by compound-specific isotope ratio mass spectrometry.

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More information

Accepted/In Press date: 22 March 2018
e-pub ahead of print date: 28 March 2018
Published date: July 2018

Identifiers

Local EPrints ID: 437528
URI: http://eprints.soton.ac.uk/id/eprint/437528
ISSN: 0146-6380
PURE UUID: 8fb42cad-4482-4cc1-a9a8-10c2337a5266
ORCID for Gordon N. Inglis: ORCID iD orcid.org/0000-0002-0032-4668

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Date deposited: 04 Feb 2020 17:30
Last modified: 17 Mar 2024 04:00

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Contributors

Author: Sabine K. Lengger
Author: Paul A. Sutton
Author: Steven J. Rowland
Author: Sarah J. Hurley
Author: Ann Pearson
Author: B. David A. Naafs
Author: Xinyue Dang
Author: Richard D. Pancost

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