Clay-organic associations in marine sediments: carbon, nitrogen, and amino acids in the fine

183 Pages·2011·2.49 MB·English

AN ABSTRACT OF THE THESIS OF
Karen Weliky for the d.gree of Master of Science
in Oceanography presented on 5 August 1982
Title: Clay-Organic ssociations in Marine Sediments: Carbon,
Nitrogen, and Pmino Acids in the fine grained fractions
Redacted for privacy
Abstract approved:
Erwin Suess
Previous work by other researchers has indicated that organic
molecules can be taken up from solution and complexed to clay mineral
external and internal surfaces. This can increase the concentration
and stability of organic molecules in soils, marine
sediments, and water column particulates. In addition, clay mineral
surfaces may facilitate the vertical and horizontal transport, by
wind and water, of adsorbed organic matter.
Five sediment samples, collected from diverse sedimentary environ-
ments, were divided into 6 different size fractions ranging from
approximately 0.2 to 5.0 micrometers in diameter. In order to better
define the composition and cuantity of organic matter associated with
clay mineral surfaces, organic carbon and nitrogen concentrations,
clay mineral compositions, and surface areas were determined for each
size fraction. Previous studies suggest that nitrogen-rich organic
matter, possibly amino compounds, are most readily complexed to clay
mineral surfaces. Therefore the composition and quantity of amino acids
and amino sugars were also determined in each sediment size fraction.
The amount of organic carbon, nitrogen, and amino acids increased
with decreasing size fraction and increasing clay content in all samples.
The relationship between organic constituents and specific surface
area of the size fractions indicate that most of the organic matter
present is associated with mineral surfaces.
Changes in the composition of the organic matter in the different
size fractions were most evident in the red clay sample where the
organic matter/clay ratio is low and detrital organic input is minimal.
The C-org/N-org ratio decreased with decreasing size fraction sug-
gesting that a relatively more N-rich organic component is concentrated
in the smaller size fractions. An increase in the concentrations of
-aianine, 1-aminobutyric acid, lysine, arginine, and histidine were
also correlated with a decrease in organic carbon content in the red
clay sample, implying that these amino acids compose a residual organic
fraction, perhaps sorbed to clay minerals, which is evident nly when
other organic carbon-rich compounds are absent. Regional variations
in amino acid compositions and organic matter content between the
different samples suggest that the relative concentrations of indivi-
dual amino acids may be indicators of the degree of organic matter
degradation and stabilization in the sediment.
CLAY-ORGANIC ASSOCIATIONS IN MARINE SEDIMENTS:
CARBON, NITROGEN, AND AMINO ACIDS
IN THE FINE GRAINED FFCTIONS
by
Karen Weliky
A THESIS
submitted to
Oregon State University
in partial fulfillment of
the requirements for the
degree of
Master of Science
June 1983
APPROVED:
Redacted for privacy
Professor of Oceanography in charge of major
Redacted for privacy
Dean o
Redacted for privacy
Dean of Graduate School
Date thesis presented 5 August 1982
Typed by Karen Weliky for Karen Wel
For Mom, Dad,
and Michael
Tres modtre
i
a .-L -. a. t
'3 3
I-. - L
p
Ret en u
-Th,_
=:=
:- p
p r:=Z
Syrinx
Claude Debussy
AQQIOWLEDGEMENTS
There are many people to thank for helping me along this three year
journey. First of all my advisor, Erwin Suess, who went out of his way
to open doors and provide me with every opportunity to get the maximum
experience and education during my years here. Thanks for your
encouragement,confidence, and friendship, and for providing a good
example to follow -- both as a creative scientist and as a human being.
Thank you to the other members of my committee, Julius Dasch,
Jack Dymond, and Susan Stafford, for very helpful comments and for
making the thesis defense questioning period an enjoyable experience.
Nick Pisias also offered valuable comments on the mineralogy paper
(chapter III).
Peter Muller, at the University of Kiel, W. Germany, spent many
weeks working with and without me on the amino acid analyses. I am
very grateful. I am also grateful to Roy Carpenter of the University
of Washington for arranging for me to use their surface area analyzer.
And to George Keller, Mitch Lyle, Kim Jones, and an anonymous person
on the W8l03 cruise who collected and froze sediment cores for me.
Becky Simpkins hurriedly and good naturedly typed last minute pages
for me. Carolyn Lupoli was very helpful when it came time to
reduce-and--Xerox. Ed Howes did a beautiful job of drafting my figures.
I am grateful to Kathy Fischer and Andy Ungerer for their work
on the often frustrating LECO carbon technique. Andy patiently
endured my outbursts of frustration and provided much help and advice
in the lab.
I thank Mark I-lower for omelettes and for the use of his computer
terminal, Al Federman for the use of his typewriter, the boys at
Sonatech (Dale, Rand, and Milo) for the use of their printer, and
Runoff for justifying my margins.
A large hug goes to Mitch Lyle who read far more about amino
acids than he ever thought possible. Thank you for your encouragement,
as well as the time you spent proofreading and teaching me the ways"
of factor analysis.
And to Kris (Rip van) McElwee, une trs chre arnie, who shared
many relaxing hours with me and Teleman, Starnitz, and Staeps, and who
introduced me to M. Morceau de Bois. Kris along with Mitch deserve a
special award as the last minute crew, madly typing, cutting, and
pasting as the seconds ticked by.
And to Takineach Creek and the sand dune gang.
And to Heidi Powell who proofread many pages -- your friendship
and enthusiasm for life and the future are a great comfort.
And to the rest of the Seattle contingent, Larry, Cherylene, and
Andy, who provide me with a home away form home and a good supply
of oysters on the half shell.
And to Stuart Blood who typed many tables, and ho made possible
the computer generated histograms of my amino acid data. Your friendship,
support, and confidence in me often kept me going.
And to my buddy, George Redden, for your friendship, patience, guitar
duets, and scientific advice, and for sharing with me our first years
in Corvallis.
And to Tina who suggested caviar and cream cheese and who suffered
late nights with me at the office (and the Class Reunion) reinforcing
our belief in the old adage "misery loves company". --- Here's to
yours, Tina.
Aiid to so many others who made Corvallis home -- my roomate Karin
Schultz, Al "no-thank-you" Federman, Mark Hower, Joe Jennings, Bob, Sally,
and Ross Duncan, Kathy Fischer, Dave Murray, Anne Matherne, Bruce Finney,
Larry Krissek, Lisa Kaskan, Eric Olson, Bob Karlin
This work was supported by the Office of Naval Research through
grant N00014-79-C-0004, Project NR083-1026 to Oregon State University.
My work in Germany was made possible by funds from the NSF Division
of International Programs through contract 8O-WE-19.
TABLE OF CONTENTS
PREFACE
1
CHAPTER I: CLAY-ORGANIC ASSOCIATIONS IN MARINE SEDIMENTS: 2
CARBON, NITROGEN. AND AMINO ACIDS IN THE FINE
GRAINED FRACTIONS
ABSTRACT
3
INTRODUCTION
5
Mechanisms of Clay-Organic Reactions 6
Evidence for Clay-Organic Complexes in
8
Soils and Sediments
OBJECTIVES 12
METHODS 15
Size Fractionation 13
Carbon is
Nitrogen 18
Major Inorganic Element Chemistry
19
Amino Acids and Amino Sugars
Mineralogy 20
Specific Surface Area 21
RESULTS AND INTERPRETATION
22
Size Fractionation
22
Nitrogen and Carbon
24
Organic Nitrogen and Carbon
24
Size Distributions and Recovery
28
of Organic Nitrogen and Carbon
Fixed inorganic Axonium: Relationship
to Clay Minerals
Amino Acids, Amino Sugars, and Ammonia-Nitrogen
3
Source of Ammonia-Nitrogen 35
Recovery of Amino Acids After Hydrolysis
42
Organic Nitrogen and Carbon Attributed 44
to Amino Compounds
Amino-Nitrogen Reported in Other Sediments 52
Mineralogy and Surface Area: Relationship to 53
Organic Matter
Fe-Mn Oxyhydroxide Minerals in R and NC 56
Specific Surface Area: Relationship to 58
Mineralogy
Specific Surface Area: Relationship to 61
Organic Matter Composition
Quantification of Organic Matter 66
Adsorbed on Mineral Surfaces
CONCLUSIONS: EVIDENCE FOR CLAY-ORGANIC ASSOCIATIONS 69
Comparison of Samples
Sorption Mechanisms 71
Size Distributions of Organic Matter and 80
Inorganic Mineral Phases in R