Reverse search and related processing of gas chromatographic/mass spectrometric data from petroporphyrin analyses

Hein, Christopher J.; Gill, Josie; Evershed, Richard P.; Eglinton, G.

doi:10.1021/ac00286a018

Cited by 9 publications

(3 citation statements)

References 33 publications

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“…With some modifications to procedures developed for the synthesis of volatile alkyl porphyrins (Boylan, et al, 1969;Boylan and Calvin, 1967;Eckardt, et al, 1988;Gill, et al, 1986;Hein, et al, 1985;Marriott, et al, 1984) a synthetic route to volatile chlorin derivatives has been devised (figure 3.17). Methyl pyropheophorbide a (MPPBDa), a common chlorophyll a degradation product found in marine sediments, was used as a model chlorin in this work.…”

Section: Discussionmentioning

confidence: 99%

“…In brief, the hybrid procedure (Marriott, et al, 1984) consists of inserting Si into the macrocycle with hexachlorodisilane (Si2Cl6) in toluene to form the dichloro-Si(IV)-porphyrin complex, followed by hydrolysis of the axial chlorines in aqueous KOH, and silylation of the axial hydroxy groups with N-methyl-N-(tert .-butyldimethylsilyl)trifluoroacetamide (MTBSTFA) in pyridine (figure 3.1.c). Yields for this synthesis were reported to be >90% (Hein, et al, 1985).…”

Section: Porphyrinsmentioning

confidence: 90%

“…It was therefore undertaken to synthesize GC-arnenable porphyrin silicon derivatives (figure 3.1.b) in much the same manner as was done by Kenney, et al with the phthalocyanines (Boylan, et al, 1969;Boylan and Calvin, 1967). This work was expanded upon in the 1980's by Eglinton and Maxwell's group at the University of Bristol to yield a vast array of petroporphyrin structural data by analyzing GC-MS data from petroporphyrin fractions derivatized to their volatile silicon complexes (Eckardt, et al, 1988;Gilt et al, 1986;Hein, et al, 1985;Marriott, et al, 1984).…”

Section: Porphyrinsmentioning

confidence: 99%

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Nitrogen isotopes in chlorophyll and the origin of Eastern Mediterranean sapropels

Sachs¹

1997

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The goals of this thesis were: (1) to establish methods for the determination of nitrogen and carbon isotope ratios in marine particulate and sedimentary chlorophyll derivatives; (2) to establish chlorophyll ()15N and ol3C as proxies for the nitrogen and carbon isotopic composition of marine phytoplankton; and (3) to use chlorophyll nitrogen isotopic ratios to understand the origin of Late Quaternary Eastern Mediterranean sapropels.Techniques are presented for the determination of chlorin nitrogen and carbon isotopic ratios in marine particles and sediments with a precision greater than 0.15 per mil for both isotopes. The procedure can be performed in about 4 hours for particulate and 8 hours for sediment samples, and relies on multiple chromatographic purifications. About 20 g of a moderately organic-rich sediment are required.A technique is also presented for the determination of chlorin nitrogen and carbon isotopic ratios by isotope-ratio monitoring gas chromatography-mass spectrometry (irmGC-MS) by synthesizing bis-(tert.-butyldimethylsiloxy)Si(IV) chlorin derivatives. However, yields for the 4-step synthesis were only about 5-6% and there was a net isotopic depletion of 1.2 (± 0.3) per mil in the derivative, relative to the starting material.These techniques are then used to show that the nitrogen isotopic difference between chlorophyll and whole cells in six species of marine phytoplankton is 5.16 ± 2.40 per mil. For carbon, the isotopic difference between chlorophyll and whole cells in five species of marine phytoplankton is -0.02 ± 2.12 per mil. A model of the distribution of 15N in phytoplankton is constructed and it is demonstrated that the interspecies variability observed for the nitrogen isotopic difference between chlorophyll and whole cells can be attributed to differences in iii the partitioning of cellular nitrogen between non-protein biochemicals. In the field, where mixed assemblages of phytoplankton prevail, the isotopic difference beween chlorophyll and whole cells is expected to tend toward the average value of 5.16 per mil.Finally, the average nitrogen isotopic composition of chlorins from six Late Quaternary Eastern Mediterranean sapropels ( -5.01 + 0.38 per mil) was found to be very similar to the o15N of chlorophyll from the modem deep chlorophyll maximum ( -6.38 ± 1.80 per mil) in the Eastern Mediterranean. In addition, sapropel photoautotrophic material, calculated from the chlorin o15N, had the same isotopic composition (0.15 per mil) as both bulk sapropel sediments (-0.08 ± 0.53 per mil) and deep water nitrate (-0.05 per mil). These data suggest (a) that bottom waters were anoxic, (b) that organic matter burial efficiency was enhanced, and (c) that oligotrophic conditions similar to today persisted, in the Eastern Mediterranean during sapropel deposition. These results contradict earlier interpretations of Late Quaternary bulk sedimentary o15N in the Eastern Mediterranean. The latter concluded that the pattern of high o15N values in intercalated marl oozes and low values in ...

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Section: Discussionmentioning

confidence: 99%

Section: Porphyrinsmentioning

confidence: 90%

Section: Porphyrinsmentioning

confidence: 99%

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Nitrogen isotopes in chlorophyll and the origin of Eastern Mediterranean sapropels

Sachs¹

1997

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Glass capillary gas chromatography‐mass spectrometry at high temperatures. direct analysis of free base porphyrins and metal porphyrin complexes extracted from the serpiano oil shale

Blaum

Richter

Eglinton

1988

J. High Resol. Chromatogr.

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SummaryThis contribution describes GC/MS analysis of natural petroporphyrin extracts containing alkylporphyrins either as vanadyl complexes or as demetalated free bases. The combination of high temperature glass capillary gas chromatography with mass spectrometry allows, for the first time, direct determination of electron impact mass spectra of separated alkylporphyrins, making additional purification and derivatiration unnecessary. The separation is carried out on glass capillary columns coated with the high temperature-stable medium polar, OH-terminated, polysiloxane phases PS 086 and OV-225-OH. The paper gives detailed working directions for the preparation of the high temperature GC/MS-interface, and of the high temperature stable OV-225-OH columns (max. working temperature 390°C).

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Multimolecular data processing and display in organic geochemistry: The evaluation of petroporphyrin GC-MS data

Eckardt

Dyas

Yendle

et al. 1988

Organic Geochemistry

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Reverse search and related processing of gas chromatographic/mass spectrometric data from petroporphyrin analyses

Cited by 9 publications

References 33 publications

Nitrogen isotopes in chlorophyll and the origin of Eastern Mediterranean sapropels

Nitrogen isotopes in chlorophyll and the origin of Eastern Mediterranean sapropels

Glass capillary gas chromatography‐mass spectrometry at high temperatures. direct analysis of free base porphyrins and metal porphyrin complexes extracted from the serpiano oil shale

Multimolecular data processing and display in organic geochemistry: The evaluation of petroporphyrin GC-MS data

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