Chromatographic Enrichment and Subsequent Separation of Nickel and Vanadyl Porphyrins from Natural Seeps and Molecular Characterization by Positive Electrospray Ionization FT-ICR Mass Spectrometry

Putman, Jonathan C.; Rowland, Steven M.; Corilo, Yuri; McKenna, Amy M.

doi:10.1021/ac502672b

Cited by 46 publications

(62 citation statements)

References 56 publications

(114 reference statements)

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“…It can also be seen from Figure 3 that F Ni contains the most abundant S x O y compounds. This phenomenon is also observed for vanadyl porphyrins-enriched fraction in the study of Putman et al [22] .…”

Section: Metal Content Analysis and Uv-vis Spectroscopysupporting

confidence: 68%

“…Additionally, Figure 5 shows that a considerable proportion of N 4 VOS species present a DBE value of 21. N 4 VOS porphyrins with DBE of 19, 20 and 21 are also detected and present high abundance by Putman et al [22] . This cannot be explained by the benzothiophene addition, indicating that other structures could exist.…”

Section: Vanadyl Porphyrin Structural Diversity Identified By Esi Ft-mentioning

confidence: 91%

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Characterization of Vanadyl and Nickel Porphyrins Enriched from Heavy Residues by Positive-Ion Electrospray Ionization FT-ICR Mass Spectrometry

Liu

Wang

et al. 2015

Energy Fuels

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Petroporphyrins were enriched and purified from atmospheric residues of two typical heavy oils, Canadian oil sand bitumen (OSAR, Ni: 80 ppm, V: 190 ppm, S: 3.97 wt%) and Chinese Liaohe heavy oil (LHAR, Ni: 68.7 ppm, V: 1.81 ppm, S: 0.36 wt%) by silica gel chromatography. The separation and purification were confirmed by atomic absorption spectroscopy (AAS) combined with UV-vis spectroscopy, and the petroporphyrins were characterized by positive-ion electrospray ionization (ESI) Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS). Vanadyl and nickel porphyrins in OSAR are simultaneously identified by mass measurement and isotopic fine structure. Vanadyl porphyrins with structures of N 4 VO, N 4 VO 2 and N 4 VOS are all detected as protonated analyte ([M+H] + ). Both molecular ion (M +• ) and analyte ([M+H] + ) as well as their corresponding isotopes are observed for N 4 Ni porphyrins in OSAR and LHAR with an average mass resolving power of over 400 000 (m/∆m 50% ). This is rarely detected by FT-ICR MS using ESI technique previously. Formation of molecular ion can be attributed to the low oxidation potential of nickel porphyrins, effect of oil matrix on the solution conductivity and the relatively low flow rate of solution into the capillary. Three more highly unsaturated types of N 4 VO porphyrins were identified in addition to the six well-documented structures. Compared to N 4 VO porphyrins, N 4 VOS porphyrins present higher DBE ranging from 21 to 27 while N 4 VO 2 porphyrins show lower DBE ranging from 18 to 20 and narrower carbon number distribution, suggesting possible different origins of sulfur (pyrolysis of kerogen) and oxygen (diagenesis of chlorophyills). Ni/V and ratio of relative abundance of ETIO porphyrins to DPEP porphyrins (∑ETIO/∑DPEP) for nickel porphyrins indicate that Liaohe oil and Canadian oil sand bitumen are continental and marine sediment, respectively, and Liaohe oil has a higher maturity.Enrichment by the simple chromatographic method facilitates the mass spectral identification of nickel porphyrins even for heavy residue with low content of nickel and high content of sulfur.

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Section: Metal Content Analysis and Uv-vis Spectroscopysupporting

confidence: 68%

Section: Vanadyl Porphyrin Structural Diversity Identified By Esi Ft-mentioning

confidence: 91%

Characterization of Vanadyl and Nickel Porphyrins Enriched from Heavy Residues by Positive-Ion Electrospray Ionization FT-ICR Mass Spectrometry

Liu

Wang

et al. 2015

Energy Fuels

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“…[25][26][27][28] FT-ICR MS coupled with atmospheric pressure photoionization (APPI) or electrospray ionization (ESI) has been used to characterize nickel and vanadyl porphyrins from heavy petroleum crude oil and natural seeps. 12,15,[29][30][31][32][33][34] Here, we apply electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) to identify organometallic complexes, specifically iron-containing porphyrins, for the first time within algal HTL biocrudes. These compounds are responsible for bed plugging observed during hydrotreatment of the algae HTL biocrude.…”

Section: Introductionmentioning

confidence: 99%

Impact of iron porphyrin complexes when hydroprocessing algal HTL biocrude

Jarvis

Sudasinghe

Albrecht

et al. 2016

Fuel

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We apply Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) for direct characterization of iron-porphyrins in hydrothermal liquefaction (HTL) biocrude oils derived from two algae: Tetraselmis sp. and cyanobacteria. The iron porphyrin compounds are shown to cause catalyst bed plugging during hydroprocessing due to iron deposition. Inductively-coupled plasma optical emission spectrometry (ICP-OES) was utilized for iron quantitation in the plugged catalyst beds formed through hydroprocessing of the two HTL biocrudes and identifies an enrichment of iron in the upper five centimeters of the catalyst bed for Tetraselmis sp. (Fe=100,728 ppm) and cyanobacteria (Fe=115,450 ppm). Direct infusion FT-ICR MS analysis of the two HTL biocrudes with optimized instrument conditions facilitates rapid screening and identification of iron porphyrins without prior chromatographic separation. With FT-ICR MS we identify 138 unique iron porphyrin compounds in the two HTL biocrudes that have similar carbon number and double bond equivalent distributions to the metal porphyrins (e.g. Ni and V) reported for petroleum. No iron porphyrins are observed in the cyanobacteria HTL biocrude after hydroprocessing, which indicates that iron porphyrin structures in the HTL biocrude are degraded during hydrotreatment. Hydrodemetallization reactions that occur through hydroprocessing of HTL biocrudes could be responsible for the decomposition of iron porphyrin structures leading to metal deposition in the catalyst bed that result in catalyst deactivation and bed plugging, and must be addressed for effective upgrading of algal HTL biocrudes.

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“…In general, petroleum porphyrins exist in homologous manifolds of several structural classes and can manifest great structural diversity. A series of papers nowadays is devoted to the determination of various vanadyl porphyrins (VP), to application of state-of-the-art massspectroscopic techniques for that purpose as well as to the development of different pathways of the effective vanadyl extraction [1,4,[16][17][18][19][20][21][22][23]. Dickie and Yen were the first to suggest that, having many of the same interactive groups as asphaltenes, petroporphyrins could also play a role in asphaltene self-assembly, adsorption, and phase separation [24].…”

Section: Introductionmentioning

confidence: 99%

High-Field (3.4 T) ENDOR Investigation of Asphaltenes in Native Oil and Vanadyl Complexes by Asphaltene Adsorption on Alumina Surface

et al. 2019

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Vanadyl porphyrin complexes in asphaltenes from heavy (Karmalinskoye) oil and in asphaltene films obtained as a result of adsorption on the surface of aluminum oxide were studied by electron paramagnetic resonance (EPR) and double electron-nuclear resonance (ENDOR) in the W-band frequency range (microwave frequency of 95 GHz, magnetic field of 3.4 T). Mims ENDOR spectra from 1H and 27Al nuclei are observed. ENDOR spectra are different for native oil and asphaltenes from one side and the adsorbed samples from the other side while no significant changes in X- (microwave frequency of 9 GHz) or W-band EPR spectra are found. The results allow supposing that vanadyl porphyrin complexes (at least in the studied asphaltene films) participate in the formation of asphaltene aggregates through the functional groups rather than π−π interactions. The data show the feasibility of the commercial pulsed ENDOR approaches for the investigation of crude oils and their constituents under external influence.

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Chromatographic Enrichment and Subsequent Separation of Nickel and Vanadyl Porphyrins from Natural Seeps and Molecular Characterization by Positive Electrospray Ionization FT-ICR Mass Spectrometry

Cited by 46 publications

References 56 publications

Characterization of Vanadyl and Nickel Porphyrins Enriched from Heavy Residues by Positive-Ion Electrospray Ionization FT-ICR Mass Spectrometry

Characterization of Vanadyl and Nickel Porphyrins Enriched from Heavy Residues by Positive-Ion Electrospray Ionization FT-ICR Mass Spectrometry

Impact of iron porphyrin complexes when hydroprocessing algal HTL biocrude

High-Field (3.4 T) ENDOR Investigation of Asphaltenes in Native Oil and Vanadyl Complexes by Asphaltene Adsorption on Alumina Surface

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