Unprecedented Ultrahigh Resolution FT-ICR Mass Spectrometry and Parts-Per-Billion Mass Accuracy Enable Direct Characterization of Nickel and Vanadyl Porphyrins in Petroleum from Natural Seeps

McKenna, Amy M.; Williams, Jeffrey T.; Putman, Jonathan C.; Aeppli, Christoph; Reddy, Christopher M.; Valentine, David L.; Lemkau, Karin L.; Kellermann, Matthias Y.; Savory, J.; Kaiser, Nathan K.; Marshall, Alan G.; Rodgers, Ryan P.

doi:10.1021/ef5002452

Cited by 93 publications

(100 citation statements)

References 83 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…run data. In addition to polar compound distribution that is similar to that previously described for algal HTL biocrudes ( Figure A2), 40,41 Table 3) 12,15,33,34 , mass spectrometry does not differentiate isomers, therefore it is possible that the algal HTL oil porphyrins are different isomers than those found in petroleum. are not unique to the two HTL biocrudes discussed thus far ( Figure A4, Table A2).…”

Section: Resultssupporting

confidence: 64%

“…[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%

See 1 more Smart Citation

Impact of iron porphyrin complexes when hydroprocessing algal HTL biocrude

Jarvis

Sudasinghe

Albrecht

et al. 2016

Fuel

View full text Add to dashboard Cite

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.

show abstract

Section: Resultssupporting

confidence: 64%

Section: Introductionmentioning

confidence: 99%

Impact of iron porphyrin complexes when hydroprocessing algal HTL biocrude

Jarvis

Sudasinghe

Albrecht

et al. 2016

Fuel

View full text Add to dashboard Cite

show abstract

“…The resolution and sensitivity of FT-ICR MS enabled studies and characterization of a number of complex mixtures, e.g., natural organic matter (NOM) [5, 23, 24], and many -omics sciences have emerged such as metabolomics [25], petroleomics [26, 27], and even “foodomics” [28], looking at complex food products, including vegetable oil [29], beer [30], wine [12, 31–33], champagne [34, 35], and whisky [22]. A typical analysis by FT-ICR MS consists of acquiring electrospray ionization (ESI) or matrix-assisted laser desorption/ionization (MALDI) mass spectra, determination of the molecular formulae of the observed peaks—usually by Kendrick mass defect analysis [36–38]—and production of van Krevelen diagrams [37, 39, 40] to visualize the distribution of elemental compositions in the sample.…”

Section: Introductionmentioning

confidence: 99%

Chemical Diversity and Complexity of Scotch Whisky as Revealed by High-Resolution Mass Spectrometry

Kew

Goodall

Clarke

et al. 2016

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

Scotch Whisky is an important product, both culturally and economically. Chemically, Scotch Whisky is a complex mixture, which comprises thousands of compounds, the nature of which are largely unknown. Here, we present a thorough overview of the chemistry of Scotch Whisky as observed by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Eighty-five whiskies, representing the majority of Scotch Whisky produced and sold, were analyzed by untargeted high-resolution mass spectrometry. Thousands of chemical formulae were assigned for each sample based on parts-per-billion mass accuracy of FT-ICR MS spectra. For the first time, isotopic fine structure analysis was used to confirm the assignment of high molecular weight CHOS species in Scotch Whisky. The assigned spectra were compared using a number of visualization techniques, including van Krevelen diagrams, double bond equivalence (DBE) plots, as well as heteroatomic compound class distributions. Additionally, multivariate analysis, including PCA and OPLS-DA, was used to interpret the data, with key compounds identified for discriminating between types of whisky (blend or malt) or maturation wood type. FT-ICR MS analysis of Scotch Whisky was shown to be of significant potential in further understanding of the complexity of mature spirit drinks and as a tool for investigating the chemistry of the maturation processes. Graphical Abstractᅟ Electronic supplementary materialThe online version of this article (doi:10.1007/s13361-016-1513-y) contains supplementary material, which is available to authorized users.

show abstract

“…Chromatographic separation combined with electrospray ionization mass spectral characterization (ESIMS) provides molecular weights for metal-containing compounds based on peak coherence between chromatographic features that match the isotopic fine structure of metals such as Fe, Cu and Ni (Mounicou et al, 2009;Baars et al, 2014Baars et al, , 2015Boiteau and Repeta, 2015). Finally, high mass accuracy Fourier transform ion cyclotron resonance mass spectrometry (FT-ICRMS) can achieve resolving power and mass accuracy sufficient to assign elemental formulas to metal containing compounds (McKenna et al, 2014;Waska et al, 2015).…”

mentioning

confidence: 99%

Structural Characterization of Natural Nickel and Copper Binding Ligands along the US GEOTRACES Eastern Pacific Zonal Transect

et al. 2016

Self Cite

View full text Add to dashboard Cite

Organic ligands form strong complexes with many trace elements in seawater. Various metals can compete for the same ligand chelation sites, and the final speciation of bound metals is determined by relative binding affinities, concentrations of binding sites, uncomplexed metal concentrations, and association/dissociation kinetics. Different ligands have a wide range of metal affinities and specificities. However, the chemical composition of these ligands in the marine environment remains poorly constrained, which has hindered progress in modeling marine metal speciation. In this study, we detected and characterized natural ligands that bind copper (Cu) and nickel (Ni) in the eastern South Pacific Ocean with liquid chromatography tandem inductively coupled plasma mass spectrometry (LC-ICPMS), and high-resolution electrospray ionization mass spectrometry (ESIMS). Dissolved Cu, Ni, and ligand concentrations were highest near the coast. Chromatographically unresolved polar compounds dominated ligands isolated near the coast by solid phase extraction. Offshore, metal and ligand concentrations decreased, but several new ligands appeared. One major ligand was detected that bound both Cu 2+ and Ni 2+ . Based on accurate mass and fragmentation measurements, this compound has a molecular formula of [C 20 Ni] + were determined for two of these compounds. Addition of Cu and Ni to the samples also revealed the presence of additional compounds that can bind both Ni and Cu. Although these specific compounds represent a small fraction of the total dissolved Cu and Ni pool, they highlight the compositional diversity and spatial heterogeneity of marine Ni and Cu ligands, as well as variability in the extent to which different metals in the same environment compete for ligand binding.

show abstract

Unprecedented Ultrahigh Resolution FT-ICR Mass Spectrometry and Parts-Per-Billion Mass Accuracy Enable Direct Characterization of Nickel and Vanadyl Porphyrins in Petroleum from Natural Seeps

Cited by 93 publications

References 83 publications

Impact of iron porphyrin complexes when hydroprocessing algal HTL biocrude

Impact of iron porphyrin complexes when hydroprocessing algal HTL biocrude

Chemical Diversity and Complexity of Scotch Whisky as Revealed by High-Resolution Mass Spectrometry

Structural Characterization of Natural Nickel and Copper Binding Ligands along the US GEOTRACES Eastern Pacific Zonal Transect

Contact Info

Product

Resources

About