Application of metalloporphyrin biomarkers as petroleum maturity indicators: The importance of quantitation

Baker, Earl W.; Louda, J. William; Orr, Wilson L.

doi:10.1016/0146-6380(87)90041-6

Cited by 23 publications

(15 citation statements)

References 17 publications

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“…In contrast to MEM, deriving from cyanobacterial or algal Chl-a in surface waters, MPM is thought to largely derive from anoxygenic phototrophs thriving at a deeper chemocline. In contrast to MBM, which can only derive from anoxygenic phototrophs, but whose abundances were too low to allow for the reliable determination of δ 15 N values in the here studied samples, MPM can theoretically represent a mixture of anoxygenic phototroph-derived MPM and an additional MPM-component deriving from Chl-a by phytyl ester hydrolysis and reduction of the resulting C-3 acid (Baker et al, 1987;Verne-Mismer et al, 1986). In principle, the relative contribution of anoxygenic phototrophs engaging in the rTCA cycle for carbon fixation to the pool of fossil MPM can be recognized on the basis of 'heavy' δ 13 C values.…”

Section: Nitrogen Isotopes and Nutrients At The Chemocline: Ammonium Assimilationmentioning

confidence: 78%

“…LC-UVvis and LC-MS revealed the presence of intact porphyrin molecules in 18 of the 27 studied samples, with only vanadylcomplexed species and both DPEP (deoxophylloerythroetioporphyrins) and Etio (etioporphyrins) structures being present (Figure 3), which are characterised by a closed or opened pentacyclic ring, respectively. Given the conversion of DPEP to Etio during thermal maturation (Baker et al, 1987), we conclude that the observed VO-porphyrin dominance throughout the Ediacaran SOSB sedimentary sequence (Table 1) is not due to thermal destruction of the generally more labile Ni-porphyrins (Baker et al, 1987) but rather points to environmental conditions: sulfidic bottom waters in the SOSB may have periodically removed any available nickel by precipitation as insoluble sulfides (Lewan, 1984) and left an excess of vanadium to react with labile organic matter. On the basis of observed concentrations, only VO-chelates underwent detailed characterization as intact porphyrins.…”

Section: Intact Preserved Neoproterozoic Porphyrinsmentioning

confidence: 88%

“…Nitrogen in sedimentary porphyrins that represent the diagenetic product of chlorophylls is not only covalently bound and resistant to diagenetic overprinting, but also highly source-specific ). Yet the sensitivity of porphyrins to geothermal heating precludes their survival in most Precambrian rocks that have experienced deep burial (Baker et al, 1987). The South Oman Salt Basin (SOSB; Figure 1) hosts one of the most complete and thermally best preserved Ediacaran sedimentary sequences (Figure 2; Fike et al, 2006;Amthor et al, 2003;Grosjean et al, 2009) that was initially deposited under open marine conditions (Nafun Group) and subsequently in a restricted but marine fed epicratonic basin (Ara Group), witnessing periodic transgressive cycles that led to the deposition of six (A0-A5) shallow water carbonate-evaporite couplets (Amthor et al, 2003;Mattes and Conway-Morris, 1990).…”

Section: Introductionmentioning

confidence: 99%

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Redox-Controlled Ammonium Storage and Overturn in Ediacaran Oceans

et al. 2021

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As a key nutrient, nitrogen can limit primary productivity and carbon cycle dynamics, but also evolutionary progress. Given strong redox-dependency of its molecular speciation, environmental conditions can control nitrogen localization and bioavailability. This particularly applies to periods in Earth history with strong and frequent redox fluctuations, such as the Neoproterozoic. We here report on chlorophyll-derived porphyrins and maleimides in Ediacaran sediments from Oman. Exceptionally light δ15N values (< –10‰) in maleimides derived from anoxygenic phototrophs point towards ammonium assimilation at the chemocline, whereas the isotopic offset between kerogens and chlorophyll-derivatives indicates a variable regime of cyanobacterial and eukaryotic primary production in surface waters. Biomarker and maleimide mass balance considerations imply shallow euxinia during the terminal Ediacaran and a stronger contribution of anoxygenic phototrophs to primary productivity, possibly as a consequence of nutrient ‘lockup’ in a large anoxic ammonium reservoir. Synchronous δ13C and δ15N anomalies at the Ediacaran–Cambrian boundary may reflect one in a series of overturn events, mixing ammonium and isotopically-light DIC into oxic surface waters. By modulating access to nitrogen, environmental redox conditions may have periodically affected Ediacaran primary productivity, carbon cycle perturbations, and possibly played a role in the timing of the metazoan radiation across the terminal Ediacaran and early Cambrian.

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Section: Nitrogen Isotopes and Nutrients At The Chemocline: Ammonium Assimilationmentioning

confidence: 78%

Section: Intact Preserved Neoproterozoic Porphyrinsmentioning

confidence: 88%

Section: Introductionmentioning

confidence: 99%

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Redox-Controlled Ammonium Storage and Overturn in Ediacaran Oceans

et al. 2021

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“…13,16 Very early, mass spectrometry provided invaluable insight into the molecular diversity of petroporphyrins compositions and structures. 1,4,5,18,19 In parallel, other analytical methods such as nuclear magnetic resonance (NMR) spectroscopy 19 and crystallography 20 afforded valuable insights on the structures of purified samples and, more recently, direct molecular imaging with atomic force microscopy molecular imaging. 21 A recent article introduces the phrase "metalopetroleomics" and provides a comprehensive review on fractionation and characterization of petroleum asphaltenes to study metalloporphyrins.…”

Section: ■ Introductionmentioning

confidence: 99%

Advances and Challenges in the Molecular Characterization of Petroporphyrins

et al. 2021

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Petroporphyrins, geoporphyrins, or metalloporphyrins are the original petroleum biomarkers, identified by Alfred Treibs more than a century ago and the first molecular evidence for the biogenic origins of petroleum. Since discovery, analytical strategies have been developed to identify porphyrins in petroleum and its fractions. This review focuses on the advances enabled by ultrahigh resolving power Fourier transform ion cyclotron resonance mass spectrometry in tribute to Professor Alan G. Marshall.

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“…Nickel and vanadyl PPs are the primary types of metalloporphyrins in crude oils due to their inherent thermodynamic stability. − Despite the crude oil maturation process, PPs include a substituted biogenic tetrapyrrole core yielding a series of polydisperse families with diverse double bond equivalents (DBEs), including etioporphyrins (Etio, DBE = 17), deoxophylloerythroetioporphyrins (DPEP, DBE = 18), dicyclic deoxophylloerythroetioporphyrins (Di-DPEP, DBE = 19), rhodo-etioporphyrins (Rhodo-Etio, DBE = 20), rhodo-deoxophylloerythroetioporphyrins (Rhodo-DPEP, DBE = 21), and rhodo-dicyclicdeoxophylloerythroetio (Rhodo-Di-DPEP, DBE = 22) . Isolation of Ni and V porphyrin enriched fractions from crude oils involves complex separation protocols, typically chromatography based. , …”

Section: Introductionmentioning

confidence: 99%

Effect of the Ionization Source on the Targeted Analysis of Nickel and Vanadyl Porphyrins in Crude Oil

et al. 2021

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We compare the performance of atmospheric pressure photoionization (APPI), laser desorption ionization (LDI), and electron-transfer matrix-assisted laser desorption ionization (ET-MALDI) for the analysis of petroporphyrin (PP)-enriched extracts. APPI, one of the most used ionization sources for crude oil analysis because of its low matrix and ion suppression effects, provides a broad picture of the crude oil extract, including PPs. APPI analysis resulted in a complex spectrum with more than 12000 radical cations where signals from high ionization energy (IE) species with abundant heteroatoms (N x O y S z ) predominate, masking the PP target group. LDI shows species with aromatic cores or conjugated functionalities particularly susceptible to UV laser excitation and ionization. A reduction in N-containing compounds (N x O y , N x S z ) and an increase in PPs signals indicate some selectivity in LDI. ET-MALDI resulted in a less complex spectrum with 3500 radical cations mainly from aromatic species, including NiPP and VOPPs. PPs’ selective ionization in ET-MALDI occurs via thermodynamically favored charge exchange reactions between the matrix radical cations and the analytes. ET-MALDI results in fewer ions per nominal mass than APPI and LDI, a situation benefiting signal resolution and mass accuracy in FT-ICR-MS. Identifying more than 350 PPs in crude oils (N4VO, N4VO2, N4VO3, N4VOS, and N4Ni) was possible by combining isotopic structure analysis and data refinement using the Kendrick mass defect (KMD) plots. The PP compositional space in ET-MALDI includes 269 species corresponding to N4VO and N4Ni classes, in contrast with 65 in APPI and 53 LDI. The compound classes N4VOS, N4VO2, and N4VO3 were not observed in APPI or LDI.

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Application of metalloporphyrin biomarkers as petroleum maturity indicators: The importance of quantitation

Cited by 23 publications

References 17 publications

Redox-Controlled Ammonium Storage and Overturn in Ediacaran Oceans

Redox-Controlled Ammonium Storage and Overturn in Ediacaran Oceans

Advances and Challenges in the Molecular Characterization of Petroporphyrins

Effect of the Ionization Source on the Targeted Analysis of Nickel and Vanadyl Porphyrins in Crude Oil

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