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The role of sulfur in the preservation of isoprenoid hydrocarbons in sedimentary materials of the Washington continental margin

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Title The role of sulfur in the preservation of isoprenoid hydrocarbons in sedimentary materials of the Washington continental margin
Names Pinto Alvarez, Luis A. (creator)
Prahl, Fredrick G. (advisor)
Date Issued 1993-09-23 (iso8601)
Note Graduation date: 1994
Abstract A systematic study of highly branched isoprenoids (HBI) was carried out in
suspended particulate material (SPM) and Washington coastal sediments to determine
their origin and fate. SPM collected at 10 m depth was filtered through Nitex
membranes. C₂₅ HBI were found only in the 1.2-40 μm range over the shelf. The
particle size fractionation of SPM shows different enrichment for HEH, a common
hydrocarbon in phytoplankton, and the sum of C₂₅ HBI in the finer fractions suggesting
these hydrocarbons do not share a common source. The distribution of C₂₅ and C₃₀ HBI
correlates with the chlorophyll maxima suggesting an upper-water microbial source
associated with phytoplankton biomass.
It has been hypothesized that sulfur addition into specific biomarkers occurs
during the early stages of diagenesis. Incorporation of the HBI into a refractory
geomacromolecule via a sulfur linkage or formation of HBI-thiophenes are not evident
in the sedimentary lipids. HBI show a rapid decrease in concentration with depth in both
midshelf and slope sediments suggesting that biodegradation is the major pathway for
their disappearance in Washington coastal sediments.
Sediment cores from a midshelf and slope locations show the existence of
suboxic/anaerobic conditions within the first 5 cm in the sediments. Elemental sulfur
distribution in the midshelf appears to be controlled by bioturbation. On the slope, its
profile indicates a quasi steady state regime.
Phytane and phytenes (∑Phy) are the major products of Raney nickel
desulfurization in both midshelf and slope sediments. Spinach and a strain of Emiliana
huxleyi treated with Raney nickel showed strikingly similar patterns to the
desulfurization products of sedimentary lipids. The amount of ∑Phy in the slope
decreases abruptly by a factor of 6 in the top 2 cm and gradually increases with depth.
These results are interpreted as phytyl coming from two sources: (1) chlorophyll-a and
(2) S-bound to geomacromolecules. Partial released of phytyl moieties from chlorophyll-a
warrants a reevaluation of Raney nickel as a selective desulfurizing agent before its
application for paleoenvironmental reconstruction.
Reducing micro-environments appear to exist within the bioturbated zone in shelf
sediments. However, there is no clear evidence for phytyl moieties S-linked to
macromolecules within the mixed layer. Results obtained during this study indicate that
sulfur incorporation to biomarkers, although present, does not represent a significant
mechanism for the preservation of organic carbon in normal marine sediments.
Genre Thesis/Dissertation
Topic Isopentenoids
Identifier http://hdl.handle.net/1957/29575

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