Normal Fatty Acids in 

Estuarine and Tidal-Marsh

Sediments of Choctawhatchee 

and Apalachee Bays,

Northwest Florida

GEOLOGICAL SURVEY PROFESSIONAL PAPER 724-B

Normal Fatty Acids in 

Estuarine and Tidal-Marsh

Sediments of Choctawhatchee 

and Apalachee Bays,

Northwest Florida

By ROBERT E. MILLER

SHORTER CONTRIBUTIONS TO GENERAL GEOLOGY

GEOLOGICAL SURVEY PROFESSIONAL PAPER 724-B

A study of the distribution of even-numbered 

normal fatty acids in four Holocene sedimentary 

environments as related to depth of burial and 

type of sediment

UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1972
UNITED STATES DEPARTMENT OF THE INTERIOR 

ROGERS C. B. MORTON, Secretary

GEOLOGICAL SURVEY 

W. A. Radlinski, Acting Director

Library of Congress catalog-card No. 70-184627

For sale by the Superintendent of Documents, U.S. Government Printing Office

Washington, D.C. 20402 - Price 30 cents (paper cover)

Stock Number 2401-1225
CONTENTS

Abstract __________________________

Introduction _______________________

Purpose and scope of report _____

Previous work _________________

Acknowledgments ______________

Field and laboratory work ___________

Sample collection and preparation 

Analytical procedure ____________

Results ________________________

Page 

Bl

1

1

1

3

3

3

3

Distribution of even-numbered normal fatty acids in 

four Holocene sedimentary environments _____

Tidal-marsh environment ____________________

Tidal-marsh-river environment ________________

Estuarine-bayou environment ____________

Estuarine environment ________________

Comparison of even-numbered normal fatty

acids in the four environments ________ _

Summary and conclusions ______________ 

References cited ____________... __________

Page

B7

7

8

9

9

9

11

11

ILLUSTRATIONS

FIGURE 1. Map showing location of Choctawhatchee Bay and Apalachee Bay areas __ _ ____ __ -

2. Map showing core sample localities in the Apalachee Bay area __ ________ _ ____ _ _________

3. Histograms showing fatty acid distribution in core samples from tidal-marsh, tidal-marsh-river, and 

estuarine-bayou environments ___________________ _.. ________ - ___ _ _____________

4. Map and histograms showing sample localities and fatty acid distribution in bottom sediments of

Choctawhatchee Bay __ - _______________________________ __ __ _ 

to shorter chain

5-7. Graphs showing:

5. Variation, with depth of burial, of ratio of longer chain

2(Ci2:o-Ci8:o) fatty acids in sediments _____ _ _____ _ _________________________

6. Plot of Ci2:o to Cie:o ratios as a function of depth of water for samples collected along an 

east-to-west traverse in Choctawhatchee Bay _____ _ ____ _ _ ______________

7. Variation, with depth of burial, of Ci2» to Cw» ratios in sediments from core samples taken 

from tidal-marsh, tidal-marsh-river, and estuarine-bayou environments _ ______________

Page

B3 

3

5

6

8

10

11

TABLE

TABLE 1. Sample localities and types, amounts of lipids and fatty acids extracted, and percentages of normal 

even-numbered fatty acids Ciz:o through CM* ____________________________ 

Page

B7

ill

SHORTER CONTRIBUTIONS TO GENERAL GEOLOGY

NORMAL FATTY ACIDS IN ESTUARINE AND TIDAL-MARSH

SEDIMENTS OF CHOCTAWHATCHEE AND APALACHEE

BAYS, NORTHWEST FLORIDA

By ROBERT E. MILLER

ABSTRACT

Normal fatty acids Ci2:o through Ca^o from four selected 

sedimentary environments were isolated and identified by 

gas chromatography. Relative abundance ratios S(C2o :o-C28:o) 

to S(Ci2:o-Cis:o) for these fatty acids were shown to vary as 

a function of depth of burial, sediment type, and depositional 

environment.

The tidal-marsh, tidal-marsh-river, estuarine-bayou, and 

estuarine sediments examined show distinct characteristic 

differences in the relative percentage abundance of the 20:0 

through Casio fatty acids. The tidal-marsh sediments contain by 

far the greatest proportions of longer chain fatty acids, C20 :o 

through C»8:o, which apparently are derived mainly from the 

terrestrial marsh plant waxes. The tidal-marsh environment, 

therefore, should be considered a significant contributor of 

lipid substances that may form high-wax petroleum accumulations in ancient nearshore brackish-marine rocks.

In cores about 3 feet long from each of three environments 

 tidal marsh, tidal marsh river, and estuarine bayou Ci6:o 

is the dominant fatty acid in the Ci2:o-Ci8:o range in the upper 

6-inch layer of surface sediments. At a depth of approximately 25 inches, Ci2:o becomes the dominant fatty acid in this 

range. In the upper 6-12 inches of bottom sediments in the 

eastern part of Choctawhatchee Bay, the fourth (estuarine) 

environment studied, Ci2:o is the dominant fatty acid, but it 

progressively decreases in relative abundance while, in turn, 

Ciero increases in relative abundance with increasing depth of 

water, bottom-water salinity, and distance from the source of 

inflowing organic matter and sediment and with decreasing 

amount of sunlight reaching the bottom sediment. Cie :o is the 

dominant fatty acid in the Ci2:o-Ci8:o range in the western part 

of the bay. Some lines of evidence support Bradley's (1970) 

bacterial inhibitor concept of lauric acid Ciaio.

INTRODUCTION 

PURPOSE AND SCOPE OF REPORT

The purpose of the present work was to determine 

the relative proportion and distribution of evennumbered saturated fatty acids Ci2:0 through C28: o 

in the sediments from four modern sedimentary

environments. Particular emphasis was placed on 

the origin of the higher molecular weight fatty acids, 

C20 :o through C28 :o. Cores were taken in three of the 

environments to determine what changes in the distribution occur with depth of burial and with sediment type to a depth of about 4 feet. Six clamshell 

grab samples from the upper 6-12 inches of sediment 

of Choctawhatchee Bay, representing the estuarinelagoonal-complex environment, were collected in 

water depths ranging from about 9 feet, in the 

eastern part of the bay, to 34 feet, in the western 

part. This study was planned for completion within 

a 1-year period, so time permitted only a few 

samples from each environment to be analyzed. The 

samples selected were chosen to be representative of 

the four environments. The conclusions reached are 

considered to be preliminary.

PREVIOUS WORK

Geochemical studies of fatty acids have been reported by several investigators. Jeffrey (1966) emphasized the distribution of fatty acids in sea water. 

Cooper (1962), Leo and Parker (1966), Parker 

(1967), and Cooper and Blumer (1968) investigated 

the occurrence of fatty acids in marine sediments. 

Peterson (1967) studied the abundance and composition of fatty acids in shallow-water marine and 

lacustrine environments. The occurrence of fatty 

acids in recent and ancient sediments and in crude 

oils has been reported by Abelson and Parker 

(1962), Cooper and Bray (1963), Van Hoeven, 

Maxwell, and Calvin (1969), and Kvenvolden (1966, 

1967) and reviewed by Eglinton (1969). The distribution of fatty acids in lipids of aquatic and terrestrial plants was reviewed by Shorland (1963). 

Breger (1968) pointed out the importance of organic

Bl
B2 SHORTER CONTRIBUTIONS TO GENERAL GEOLOGY

colloid-lipid complexing to form higher molecular 

weight precipitates in natural waters and the 

manner in which this mechanism can influence lipid 

distributions in bottom sediments.

The term "lipid" is used herein, according to the 

classification established by Bloor (1925, p. 243) 

and later reemphasized by Bergmann (1963, p. 503), 

to mean those substances that (1) are produced by 

animal, plant, and microbial organisms; (2) are 

soluble in water only with great difficulty but are 

readily extractable in the so-called fat solvents, such 

as ether, chloroform, and benzene; and (3) are 

required to be chemically defined and classified as 

demonstrating an actual or potential relationship to 

the ester of fatty acids.

Lipids, then, are classified in three major groups: 

Simple lipids. True, neutral fats, which are the fatty 

acid esters of glycerol, and true waxes, which are 

the fatty acid esters of higher aliphatic alcohols. 

Compound lipids. Compounds of fatty acids with 

alcohols but containing other organic complexing 

elements, such as phosphorus, nitrogen, and sulfur, in addition to the alcohol.

Derived lipids. Free aliphatic fatty acids, alcohols 

and hydrocarbons, and branched acyclic or cyclic 

terpenoids and steroids; derived from simple and 

compound lipids by hydrolysis. 

In this investigation I was especially concerned 

with the even-numbered saturated straight-chain 

fatty acids ranging consecutively from Ci2:0 through 

C28:0 that are generally associated with true fats, 

oils, and waxes and that have the general formula 

CnH2n+1COOH. Very little is known about the actual 

sources of the fatty acids occurring in natural sedimentary environments. A few general statements 

can be made, however, concerning the distribution 

of the saturated fatty acids occurring in plant, 

animal, and microbial organisms. According to 

Biederman (1969, p. 1500), there is little evidence 

to indicate that the fatty acids having 20 or more 

carbon atoms per molecule are major components of 

plankton or bacteria. This is substantiated by the 

work of Nagy and Bitz (1963, p. 240) and Butler, 

Downing, and Swaby (1964, p. 817), who found that 

terrestrial organic matter from higher plants contained large amounts of C20:o, C22:0, C24: o, C26: o, and 

C28:0 . Eglinton and Hamilton (1963, p. 206) reported 

that fatty acids of longer chains, C20: o through C34 :o, 

occur mainly in the plant waxes. C14:0, C16:0, and 

Ci8:o have been reported as some of the dominant 

fatty acids in bacteria as well as in plankton (Kates,

1964; Cho and Salton, 1966, p. 73; Parker and 

others, 1967, p. 707; Peterson, 1967). In some 

anaerobic bacteria, spores, fruit coat fats, and seed 

fats, the fatty acid Ci 6:0 constitutes more than 40 

percent of the saturated fatty acids present (Shorland, 1963, p. 295).

Knowledge of the distribution of saturated fatty 

acids from recent brackish-marine to less than 

normal saline coastal-marsh environments has become increasingly important in understanding the 

genesis of high-wax petroleums in ancient sediments. Hedberg (1968, p. 736) suggested thart the 

"high-wax content of crude oil appears to be related 

to genetic environment or to the kind of organic 

matter from which the oil was derived." Reed (1969, 

p. 1502) tested Hedberg's hypothesis and confirmed 

in 83 percent of the samples studied that "high-wax 

oils may reflect the contributions of terrigenous 

organic matter or of organic matter derived from 

aquatic organisms associated with waters of less than 

normal marine salinity to the genesis of petroleum." 

Reed further stated: "Thus assuming that no long 

range migration has taken place, high-wax oils 

should be associated with continental, paralic, or 

nearshore-marine deposits, and low-wax oils with 

open-marine deposits." Han, McCarthy, Van Hoeven, 

Calvin, and Bradley (1968, p. 29) and Parker and 

Leo (1965, p. 373) provided substantial support for 

the belief that although marine or nonmarine organisms may be the source materials for n-alkanes in 

the Ci2:o-Ci 7: o region, such organisms are a very 

unlikely source for any significant concentration of 

higher molecular weight n-alkanes. The evidence and 

reasoning suggest that land-plant waxes containing 

20 or more carbon atoms per molecule may be the 

source of the high-wax oils associated with nonmarine and brackish sediments. Meinschein and 

Kenny (1957) and Morrison (1969) suggested that 

plant waxes may be a source for the higher molecular 

weight fatty acids found in soils. According to 

Parker (1969, p. 364), the origin of the higher molecular weight (20-36 carbon atoms) fatty acids found 

in Holocene and ancient sediments is not yet known. 

Biederman (1969, p. 1500) indicated that "high-wax 

oils are significant because they appear to be the key 

to the origin of oil in nonmarine and brackish sediments." Biederman further stated (p. 1500) that 

saturated fatty acids with more than 20 carbon 

atoms per molecule that are found in recent soils 

and nonmarine sediments are the most likely precursors for the longer chain paraffin hydrocarbons 

and waxes in crude oil. Kvenvolden (1970) summarized the possible mechanisms by which normal
FATTY ACIDS, ESTUARINE AND TIDAL-MARSH SEDIMENTS, FLORIDA B3

fatty acids might be transformed into normal paraffin hydrocarbons. These mechanisms are thought to 

involve many reactions, including simple decarboxylations, step-by-step decarboxylation (Cooper, 

1962), hydrogenation, and cleavage. According to 

studies by Jurg and Eisma (1964), carbon addition 

might also be a significant mechanism for the generation of normal paraffin hydrocarbons.

ACKNOWLEDGMENTS

This study was carried out during 1968-69 as part 

of the National Research Council-U.S. Geological 

Survey Postdoctoral Research Associateship program.

Special thanks are given to the members of the 

organic geochemistry group, U.S. Geological Survey 

 Vernon E. Swanson, James G. Palacas, Tom G. 

Ging, Jr., Alonza H. Love, Peter M. Gerrild, and 

Frederick N. Ward for their help in collecting 

samples or in providing laboratory support facilities. 

I am especially grateful to Thomas L. Swanger for 

his valuable laboratory assistance during the summer of 1969.1 deeply appreciate the critical reviews 

of the manuscript provided by E. W. Biederman, Jr., 

Cities Service Research Co., and Wilmot H. Bradley, 

formerly with the U.S. Geological Survey.

FIELD AND LABORATORY WORK 

SAMPLE COLLECTION AND PREPARATION

The samples used in this study were taken from 

the Aucilla tidal marsh and the Econfina tidal-marsh 

river of Apalachee Bay, from Indian Bayou on the 

south side of Choctawhatchee Bay, and from the 

central parts of Choctawhatchee Bay estuary (figs.

32'

90 c

86 84' 80 e

 r

MISS j

7 I

i - "i ~f r- 1 t " 

\

ALABAMA ' GEORGIA ^

>n <. N _ i ^

II -^ 1 f

FIGURE 1. Location of Choctawhatchee Bay and 

Apalachee Bay areas.

83°52'30"

SAINT MARKS NATIONAL 

WILDLIFE REFUGE

30°00'

FIGURE 2. Core sample localities in the Apalachee Bay 

area, northwest Taylor County.

1, 2, 4). The bottom-surface sediment samples from 

the estuary and bayou were collected with a clamshell grab sampler or with a Phleger gravity corer, 

and the tidal-marsh and tidal-marsh-river samples 

were collected with hand-driven core tubes; the 

samples were frozen in dry ice immediately after 

their collection and kept frozen until prepared for 

analysis.

In the laboratory, descriptions were made of the 

fresh, moist sediment surface of the samples before 

freeze drying. The sediment samples were then 

freeze-dried to remove the interstitial water, and the 

crushed dried sediment was transferred to clean 

glass containers and stored under nitrogen.

ANALYTICAL PROCEDURE

The general procedure for sample preparation, 

extraction, purification, and analysis of fatty acids 

is summarized in the following steps:

1. Freezing of sediment sample in dry ice immediately after 

field collection.

2. Descriptions of the fresh, moist surface of the sediment 

sample in the laboratory.

3. Laboratory freeze-drying of sediment sample. Sample 

then crushed and stored under nitrogen.

4. Soxhlet solvent extraction of crushed, weighed, freezedried sediment sample in methanol and in a chloroform-methanol mixture (9:1).

5. Volume reduction of combined methanol and chloroformmethanol extracts on roto-evaporator at 45 °C.
B4 SHORTER CONTRIBUTIONS TO GENERAL GEOLOGY

6. Removal of inorganic salts and water-soluble organic 

acids by biphasic chloroform-water partitioning.

7. Drying of chloroform and soluble crude lipid extract 

over Na2SOi; volume reduction by roto-evaporation at 

45°C; evaporation to dryness under nitrogen at 30°C.

8. Determination of weight of crude lipid extract.

9. Saponification of crude lipid in 1 N methanolic KOH for 

45 minutes; extraction of nonsaponifiables with diethyl 

ether.

10. Acidification of methanolic KOH with 0.5 N HC1; extraction of fatty acids with petroleum ether.

11. Esterification of fatty acids using 14-percent BFS in 

methanol; extraction of methyl esters with petroleum 

ether.

12. Determination of weight of fatty acid methyl esters; 

confirmation of purification and completeness of esterification by thin-layer chromatography.

13. Identification of fatty acid methyl esters by gas-liquid 

chromatography.

Glass Soxhlet extraction apparatus was used during 

the entire extraction process. The Soxhlet thimbles 

were cleaned by refluxing in a methanol-chloroform 

azeotrope for 24 hours. All reagent-grade solvents 

employed in the extraction and analytical procedures 

were redistilled and dried over anhydrous sodium 

sulfate before being used, to insure quality control 

and reduce any possibility of contamination arising 

from the solvents.

Every sediment sample, each weighing 300 grams, 

was extracted for 24 hours with methanol and then 

with a chloroform-methanol mixture (9:1, v:v) for 

another 24 hours. This extraction method gave a 

solution of nonlipids and lipids (Renkonen and Varo, 

1967, p. 43). The reproducibility of the extraction 

method was confirmed by using duplicate extractions 

of split control samples.

The methanol and chloroform-methanol extracts 

were combined, and the solvent-extract volume was 

reduced to approximately 100 ml (milliliters) using 

a roto-evaporator with the temperature not exceeding 45°C. The solvent and the crude lipid extract 

were quantitatively transferred to a 250-ml separatory funnel containing 100 ml of chloroform and 20 

ml of triple-distilled water. The biphasic system was 

thoroughly agitated and allowed to separate, with 

the inorganic salts and water-soluble organic compounds favoring the aqueous layer and the lipids 

enriching the lower chloroform layer. This partitioning procedure was done three times to separate the 

lipids from the nonlipid substances. The chloroform 

and the soluble crude lipid extracts from the partitioning step were combined and dried over anhydrous sodium sulfate to remove any traces of 

occluded and entrained water remaining from the 

partition step. After removal of the water, the extract was further concentrated by removing the 

chloroform solvent using a roto-evaporator, again 

with the temperature not exceeding 45 °C. The concentrated extract was then quantitatively transferred to a previously tared and cleaned glass vial 

and evaporated to dryness under a jet of nitrogen, 

using an infrared lamp for warming at 30 °C. The 

weight of the crude lipid extract was determined, 

and then the vials were sealed under nitrogen and 

stored at 0 C C.

Preparation of the fatty acid methyl esters from 

the crude lipid extract followed the method of Metcalfe, Schmitz, and Pelka (1966). The weighed extract was quantitatively transferred to a reflux 

flask and saponified in 1 N methanolic potassium 

hydroxide for 45 minutes. The nonsaponifiable fraction, containing the hydrocarbons, sterols, and alcohols, was extracted with diethyl ether. The 

saponified fraction was acidified with 0.5 N hydrochloric acid, and the fatty acids were extracted with 

petroleum ether. The methyl esters were prepared 

by refluxing the fatty acids for 2 minutes with 14- 

percent boron trifluoride in methanol. The esterified 

mixture was diluted with saturated sodium chloride 

solution, and the methyl esters were extracted four 

times with 20 ml of petroleum ether. The extract 

was dried over anhydrous sodium sulfate and transferred to a tared vial, and its weight was determined 

after removing the petroleum ether by evaporating 

under a jet of dry nitrogen (Maurer and Parker, 

1967, p. 115). The methyl esters were then stored 

under nitrogen in 2 ml of petroleum ether.

The methyl esters were analyzed on a PerkinElmer model 900 gas-liquid chromatograph with a 

hydrogen flame detector. Matched stainless steel 

columns were used (0.093-inch I.D., 6-ft length, 

packed with 100- to 120-mesh Chromsorb 6W, with 

liquid coating of 15-percent Hi Eff 8BP). The instrument was programed to operate from an initial 

temperature of 100 °C for 3 minutes and then increase at a rate of 10 °C per minute to a final column 

temperature of 240 °C. The detector temperature 

was 330 °C.

Specific fatty acid methyl esters were identified by 

(1) comparing the retention times with standard 

methyl esters obtained from Analabs, Inc., (2) 

using internal standard "spiking" methods, and (3) 

performing preparative thin-layer chromatographic 

separations using silica gel G held on glass plates 

and a developing solvent mixture of hexane-ethanolacetic acid (85:15:1) (Malins and Mangold, 1960). 

The fatty acids were quantitatively characterized in 

their methyl ester form by planimetering the total
FATTY ACIDS, ESTUARINE AND TIDAL-MARSH SEDIMENTS, FLORIDA B5

peak areas, with a reproducibility of 0.09 square 

centimeters. They are hereafter simply referred to 

as fatty acids.

In the course of this investigation, control blanks 

were run on each solvent and on solvent extraction 

residues on the glassware to determine if artifacts 

were present. No measurable contamination could 

be determined from either the solvents or the glassware. Therefore, the qualitative and quantitative 

data that were obtained are believed to be representative of the original amounts and kinds of fatty 

acids present in the samples studied.

RESULTS

This investigation of the normal fatty acids associated with selected sedimentary environments was 

restricted to a study of the distribution of evennumbered saturated carboxylic acids ranging consecutively from C12:0 through C28:0. Table 1

summarizes the geographic localities and environments of deposition for the four sets of samples 

collected and briefly describes each sample analyzed. 

In addition, the table shows the relative abundance 

of each even-numbered fatty acid analyzed, normalized to 100 percent, and the longer to shorter chain 

ratio for each sample.

Figures 3 and 4 illustrate by histogram the distribution of the normal fatty acids according to environment of deposition, type of sediment, and depth 

of burial for the cores and grab samples collected.

Figure 5 shows the changes, with depth of burial, 

in the ratio of the sum of the percentages of the 

longer chain acids (C20 :o through 28: o) relative to 

the sum of the percentages of the shorter chain 

acids (Ci2: o through C18:0 ). Large numerical values, 

which result from a greater relative contribution of 

the higher molecular weight fatty acids, suggest the 

influence of terrestrial plant waxes. Small values,

TIDAL-MARSH ENVIRONMENT 

Aucilla River

Core depth 40 

in inches 

0

20

TIDAL-MARSH-RIVER ENVIRONMENT 

Econfina River

ESTUARINE-BAYOU ENVIRONMENT 

Indian Bayou

30 -

22

28

39

47' '

Dark-chocolatebrown mud; 

H2 S given off

121416182022242628

Core depth, 40 

in inches

°n 30

8

20

32

44

-

20 Mottled muds 

with rootmat____- -. 

_____ remnant 

reworked by 

burrowing 

organisms J£| 

o 40

£ so

i 

______________jL 20

Shells and £ 

sparse mud ce. 1° 

matrix en

^> 0

^ 40

UJ

£; so

U-

^^^ <. 10

^Shells and LU 0 

some sand ^

UJ Q- 40

30

20

./ 10

s' o

Sand and 

some shells

-

1 1

12141618202224262

-

-

12141618202224262

-

-

1

12141618202224262

-

-

1

12141618202224262 

EVEN-NUMBERED 

FATTY ACIDS

34

121416182022242628

EVEN-NUMBERED

FATTY ACIDS

FIGURE 3. Fatty acid distribution in core samples from tidal-marsh, tidal-marsh-river, 

and estuarine-bayou environments.

121416182022242628

EVEN-NUMBERED

FATTY ACIDS

443-513 0-72-2
B6 SHORTER CONTRIBUTIONS TO GENERAL GEOLOGY

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FATTY ACIDS, ESTUARINE AND TIDAL-MARSH SEDIMENTS, FLORIDA B7

TABLE 1. Sample localities and types, amounts of lipids and fatty acids extracted, and 

percentages of normal even-numbered fatty acids Cn-.» through CM: <>

Lipids Fatty Percent 2

fos/S) 1 Cj2:o Ci4io Cieio Cisio C2o' o 022:0 C2<:o C2 6:o C28 :o

Ratio

2(C2 o:-C2s:o)

S(Ci2 :o-Ci8:o)

Tidal-marsh environment, Apalaches Bay

[Core taken at surface exposed to atmosphere at low tide; SEJ^ sec. 36, T. 4 S., R. 3 E.; 100 ft due east of Aucilla River]

0-11 in. Modern living rootmat. _ --...---......- 8,640 720 4.9 2.1 5.9 3.1 13.5 4.9

11-22 in. Decomposing rootmat 1 ..... . . .. 12,320 754 7.3 3.3 5.3 3.0 20.6 6.5

22-28 in. Decomposing rootmat 2 _ ------ . 17,400 615 8.3 2.2 5.5 2.8 27.6 7.2

28-39 in. Dark-chocolate-brown mud; H S given off.. 2,999 151 14.2 4.5 20.1 4.5 12.7 7.5 

39-47 in. Tan-brown silty mud; H S given off . . - 13,100 218 18.8 3.4 10.1 4.0 24.1 8.0

14.2 

15.5 

13.3 

14.2 

12.1

29.2

24.2 

24.3 

14.8 

14.1

22.2 

14.3 

8.8 

7.5 

5.4

5.25 

4.30 

4.30 

1.30 

1.75 

3.38

Tidal-marsh-river environment, Apalachee Bay

in 3 ft of water; NEJ£ sec. 21, T. 5 S., R. 4 E.; midchannel, f Econfin

0 8 in. Mottled muds with rootmat remnant reworked by burrowing organisms. ------- 894 513 15.9 4.4 24.8 8.9 5.3 4.4

8-20 in. Shells and sparse mud matrix ------ . . 674 69.4 13.7 1.8 7.9 4.7 12.2 6.1

20-32 in. Shells and some sand.... ___ . ______ _ 648 76 28.1 1.2 10.0 6.3 7.4 5.9

32-44 in. Sand and some shells... ___ . ____ .... 588 47.7 14.7 1.7 6.3 4.2 8.4 7.2

12.4 

17.3 

12.6

17.2

15.9 

20.8 

14.8 

21.4

8.0 

15.5 

13.7 

18.9

0.85 

2.60 

1.20 

2.70 

1.84

Estuarine-bayou environment, Choctawhatchee Bay

[Core taken in 11 ft of water; lat 30°24' N., long 86°27' E.; midchannel of Indian Bayou, 1,000 ft from estuary]

0-7 in. Dark-brown homogeneous mud......... 3,300 124 5.9 2.6 11.6 5.9 3.8 4.9

7-14 in. _ .do-..- ____ .-.-. ____ ..-. _ ... 1,530 101 12.6 2.4 11.7 6.2 4.5 4.7

26-34 in. Nearly pure quartz sand containing small 

dispersed carbonaceous particles; relictbarrier-island sand.. ...-.-..--.-----. 1,140 16.4 17.3 1.0 7.2 9.1 3.4 5.9

21.5 

15.5 

14.5 

15.6

12.5

24.4 

23.6 

21.6 

15.5

16.7

19.4 

18.8 

30.7 

25.7

26.9

2.85 

2.00 

3.10 

2.50

1.85 

2.43

Estuarine environment Choctawhatchee Bay

[Grab samples of uppermost 6-12 in. of bottom sediments; lat 30°25' N., long 86°10' to 86°35' W.; east to west along axis of bay]

1. 9 ft water. Dark-brown homogeneous mud and 

minor quartz silt . __ ... 1,770 126 28.7 3.7 7.2 1.5 4.4 6.5

2.11ftwater. _ -do... __ ________ .. _ .. 1,495 103 8.8 2.2 5.2 27.6 3.7 6.3

3. 23 ft water. ....do.....-.-. ..----.- 2,120 146 27.1 11.8 27.1 15.6 2.8 4.3

4. 33 ft water, .---do----------..-.----------- 2,510 204 18.2 9.1 24.1 11.3 3.6 4.5

5. 34 ft water. __ do... ____ -. __ - __ .-.. _ 2,770 194 13.3 3.9 22.6 11.5 4.4 4.9

6. 34 ft water. __ do... ____ . ___ ______ .. 4,340 130 11.4 7.6 28.9 12.3 4.6 4.7

12.2 

12.2 

5.6 

11.4 

12.4 

9.5

20.7 

19.2 

5.7 

11.4 

15.5 

12.5

15.1

14.8 

0 

6.4 

11.5 

8.5

1.46 

1.27 

.22 

.59 

.97 

.66 

0.86

1 Microgram per gram sediment, dry weight.

2 Percentages normalized to 100 for series Ci2:o through C28=o.

resulting from more of the lower molecular weight 

fatty acids, suggest a large contribution from the 

combined sources of animal, marine phytoplankton 

and zooplankton, and terrestrial and microbial organisms. The ratio is, therefore, a measure of the 

contribution of fatty acids from plants relative to all 

sources taken together and an index for characterizing the different environments selected for study.

Table 1 shows the extractable amounts of total 

fatty acids and lipids for each sample examined. The 

tidal-marsh sediments contain two to three times 

more fatty acids than the tidal-marsh-river, 

estuarine-bayou, and estuarine sediments. The tidalmarsh sediments also contain total extractable lipids 

that are three to 15 times more abundant than in 

the tidal-marsh-river, estuarine-bayou, and estuarine 

sediments. Tidal marshes obviously are important 

contributors of fatty acids and other lipid substances 

to the subjacent sediments and therefore should be 

considered as having been potential source environments for high-wax oil accumulations in ancient 

sediments.

The sedimentary distribution, maximum and 

minimum amounts, similarities, differences, and environmental implications of the different fatty acids 

are discussed next.

DISTRIBUTION OF EVEN-NUMBERED NORMAL

FATTY ACIDS IN FOUR HOLOCENE

SEDIMENTARY ENVIRONMENTS

TIDAL-MARSH ENVIRONMENT

A core from the Aucilla tidal marsh in Apalachee 

Bay was studied to determine changes in the distribution of saturated fatty acids of marsh flora with 

depth of burial. The upper section of core was mainly 

from the modern living rootmat; this section was 

underlain successively by two separate rootmats in 

different stages of decomposition and by an interval 

of dark-chocolate-brown mud containing rootmat 

remnants which graded downward into tan-brown 

silty mud. Both mud units gave off a strong hydrogen 

sulfide odor when freshly cut. The entire core was 

free of shell organisms, and so the fatty acids,
B8 SHORTER CONTRIBUTIONS TO GENERAL GEOLOGY

ffi 10 i 

o

w 20

H 

z

D 

O 

O

o

_l

o

I

h;

^ 30

40

50

\

\

\

\^

X

-Estuarine-bayou 

environment 

(Indian Bayou)

\

Tidal-marsh-river

environment / 

(Econfina River).

Tidal-marsh 

environment 

(Aucilla River)

1.0 2.0 3.0 4.0 5.0 6.0

S(C 20:0 to C 28:0 ) 

S(Ci2:0 toC 18:0 )

FIGURE 5. Variation, with depth of burial, of ratio of 

longer chain S(C2o :o-C2s:o) to shorter chain S(Ci2!0- 

Cisro) fatty acids in sediments.

especially the longer chain acids (C20: o through 

C28 :o), are assumed to be derived mainly from the 

marsh rootmats and their decomposition products.

A comparison of the living rootmat with the decomposing rootmats and lower, mud units shows 

significant changes in the relative abundances of the 

longer chain saturated acids. The C2e:o and C28: o 

acids show progressive decreases of about twofold 

and fourfold respectively, corresponding to increasing stages of rootmat decomposition and depth of 

burial. The longer chain acid C22 :o shows about a 

twofold increase, whereas C24:0 demonstrates very 

small unsystematic changes. The C20: o fatty acid 

progressively increases in relative abundance with 

depth of burial down through the second decomposing rootmat, where it is the most abundant acid,

reaching a maximum of 27.6 percent. It decreases 

sharply in the dark-chocolate-brown hydrogen 

sulfide-bearing mud but increases sharply again in 

the tan-brown silty mud (table 1; fig. 3).

In the tidal-marsh core (table 1; fig. 3) the shorter 

chain fatty acids C14:0 and Ci8: o increase slightly in 

relative abundance with increasing depth of burial. 

The Ci2:0 and C16:0 fatty acids change significantly. 

 12:0 increases continuously; at a depth of 47 inches, 

in the tan-brown silty mud, its relative abundance 

is about four times that in the living rootmat. Ci6:0 

remains relatively constant at about 5 percent in the 

living rootmat and in the two lower, decomposing 

rootmats but increases abruptly to a maximum of 

20.1 percent in the dark-chocolate-brown mud and 

then decreases again in the 39- to 47-inch interval.

TIDAL-MARSH-RIVER ENVIRONMENT

The tidal-marsh-river core (table 1; fig. 3) illustrates the type of fatty acids produced in an environment having contributions from marine phytoplankton and zooplankton and microbial organisms as well 

as from detrital tidal-marsh flora. The upper 8 

inches of sediment in the core was mud reworked 

by burrowing organisms. It included the remnants 

of a rootmat infilled with dark-brown mud. Underlying the reworked interval was a shell zone composed of oysters and small clams in a sparse mud 

matrix. This zone graded downward into a zone of 

mixed shell fragments and sand and then into one 

containing sand and some shell debris. The most 

distinguishing characteristic of the burrowed surface zone is the relatively low proportion of the 

longer chain fatty acids (46 percent) compared with 

the shorter chain fatty acids (54 percent). The fatty 

acids C12:0, Ci4:o, Ci6:0, and C18:0 are particularly 

abundant in the surface layer. The fatty acid C12:0 

is relatively abundant throughout the core. But the 

other shorter chain fatty acids tend to decrease, and 

the longer chain fatty acids tend to increase, with 

increasing depth of burial. This is the reverse of the 

general relationship in the tidal-marsh core (table 

1; figs. 3, 5).

Biogeochemical degradation by burrowing organisms and associated bacterial activities may account 

for the high proportion of shorter chain acids in the 

surface segment of the tidal-marsh-river core. High 

percentages of longer chain acids in two of the three 

buried shell and sand intervals could result from 

periodic influxes of plant detritus carried into the 

river system during years of higher rainfall and 

runoff when mud of the two intervals was deposited.
PATTY ACIDS, ESTUARINE AND TIDAL-MARSH SEDIMENTS, FLORIDA B9

ESTUARINE-BAYOU ENVIRONMENT

A core was taken from an estuarine-bayou environment in approximately 11 feet of water in 

Indian Bayou, on the south side of Choctawhatchee 

Bay (table 1; figs. 3, 4). Sediments in this core 

consisted successively of homogeneous dark-brown 

structureless mud showing no visible evidence of 

reworking by burrowing organisms, two underlying 

decomposing rootmats, and nearly pure quartz sand 

containing small dispersed fragments of carbonaceous matter. The sand layer apparently represents a 

relict barrier island.

In the estuarine-bayou core, the shorter chain 

fatty acids C12:0 and C18:0 increase downward by 

factors of about 3 and 2 respectively, each reaching 

a maximum in the relict-barrier-island quartz sand. 

C14: o and C16: o decrease by about 1/3 and 1/3 respectively. The longer chain acids C24 :o and C26: o show a 

general decrease with depth of burial, whereas C28: o 

shows a large increase, reaches a maximum in the 

first decomposing rootmat, then decreases somewhat 

in the second decomposing rootmat and in the 

barrier-island quartz sand interval. C20:0 and C22:0 

show small, unsystematic fluctuations.

ESTUARINE ENVIRONMENT

Choctawhatchee Bay is a narrow estuarinelagoonal complex about 24 miles long and 4 miles 

wide in Walton and Okaloosa Counties (figs. 1, 4). 

Its longest axis trends east-northeast parallel to the 

Gulf of Mexico coastline. Water depth in the estuary 

is shallowest in its eastern part and increases westward to a maximum of 43 feet, near Destin Channel. 

The bay is separated from the Gulf of Mexico by 

Moreno Point barrier spit, east of the Destin Channel, and by Santa Rosa Island, a barrier island west 

of Destin Channel. The major source of sediment 

and fresh water is the Choctawhatchee River, entering the east end of the bay. Goldsmith (1966) described the type and distribution of sediments in 

Choctawhatchee Bay.

Previous organic geochemical studies in Choctawhatchee Bay and adjacent areas have been carried 

out by Swanson and Palacas (1965), Palacas, Swanson, and Love (1968), and Palacas, P. M. Gerrild, 

and Love (unpub. data). These investigations emphasized the origin, pattern of migration, deposition, 

and early diagenetic transformation of soluble humic 

substances, and the distribution of hydrocarbons in 

the estuary and adjacent subenvironments.

In the present study the relative abundances of 

the even-numbered saturated fatty acids in the 

upper 6-12 inches of the bay sediments were determined in samples collected along a line parallel to 

the long axis of the bay (fig. 4). Cores within the 

bay were not available for study of the changes in 

the fatty-acid distribution with depth of burial. The 

sediments studied consisted of dark-brown calcareous clayey muds and small amounts of fine quartz 

silt. Minute Foraminifera shells were present in all 

the samples examined. There was a noticeable absence of macroscopically visible shell fragments.

The same complete sequence of even-numbered 

normal fatty acids occurs in the bay environment as 

in the tidal-marsh, tidal-marsh-river, and estuarinebayou environments. The only exception is in sample 

3 of the bay sediments. C28:0 was not detected on repeated gas-liquid chromatographic runs of this 

sample. This lack is reflected by a low value of the 

longer to shorter chain ratio (table 1). High ratios 

of the longer to shorter chain fatty acids for samples 

1 and 2 compared with ratios for samples 4, 5, and 

6 reflect the nearness of the eastern part of the bay 

to the source of marsh flora growing upstream along 

the Choctawhatchee River and reflect the more 

favorable location of the eastern end of the bay for 

preservation of the longer chain acids because of 

faster sedimentation on the Choctawhatchee River 

delta.

COMPARISON OF EVEN-NUMBERED NORMAL FATTY 

ACIDS IN THE FOUR ENVIRONMENTS

The average ratio of longer to shorter chain fatty 

acids in the surface sediments of Choctawhatchee 

Bay (0.86) is significantly less than the average 

from the cores of the tidal-marsh river (1.84), 

estuarine bayou (2.46), and tidal marsh (3.38). This 

relation is to be expected if tidal-marsh flora is a 

major source of the longer chain fatty acids.

In the tidal-marsh core the ratios in the living and 

decomposed rootmats, dominantly composed of 

marsh plant flora, are 5.25, 4.30, and 4.30. These are 

considerably higher than the ratios in the underlying 

muds, which are 1.30 and 1.75, or the ratios in surface muds in the bayou or tidal-marsh river, which 

are 2.85 and 0.85. Seemingly, the amount and kind 

of plant detritus are the major factors in controlling 

the ratio in the surface layers.

The relative abundance of certain longer chain 

acids decreases systematically with increasing depth 

of burial in two environments: C26: o and C28:0 in the 

tidal marsh and C24: o and C26: o in the estuarine 

bayou. Peterson (1967) found a similar relation in 

two lake cores, where acids containing more than 

20 carbon atoms per molecule decreased in relative
BIO SHORTER CONTRIBUTIONS TO GENERAL GEOLOGY

abundance with increasing depth of burial. Metabolic processes of micro-organisms are a likely 

mechanism for producing these changes in the upper 

2-3 feet of sedimentary deposits.

What are considered to be postdepositional biochemically induced changes in the fatty acid distribution are exemplified by the reworked burrowed 

mottled mud and rootmat sample of the tidal-marshriver core and by the two hydrogen sulfide-bearing 

samples of the tidal-marsh core (table 1). Low proportions of longer chain acids (C20: o through C28 :o) 

occur in these three samples, all of which have obviously been subjected to biological attack. Moreover, 

these samples contain relatively high percentages of 

the C16:0 fatty acid. The normal fatty acid Ci6: o was 

most certainly present as an initial component of 

these saturated acids; however, the increased percentage of Ci 6:0 and decreased relative abundance of 

longer chain fatty acids suggest that bacteria played 

an active role in the transformation and resynthesis 

of the initial organic material, thereby increasing 

the total relative percentage of Ci6:0 in these sediments. Blumer, Chase, and Watson (1969, p. 368) 

reported that certain ammonia-oxidizing bacteria 

contain C16:0 and d6: i fatty acids as major components of their lipid cells; Saito (1960) reported that 

Ci6: o may constitute as much as 40 percent of the 

total fatty acid components in certain bacterial 

lipids; and Bloch, Baronowsky, Goldfine, Lennarz, 

Light, Norris, and Scheuerbrandt (1961, p. 921) 

found the fatty acid composition of lipids in 

anaerobically grown bacteria to be more than 40 

percent Ci6:0 .

Bradley (1970, p. 995) reported from his studies 

of the algal sediments at Mud Lake, Fla., that the 

calcium salt of the fatty acid lauric (Ci2:0 ) has a 

toxic and lethal effect on certain bacteria isolated 

from the Mud Lake sediment. [In a January 12, 

1971, letter to me, Bradley stated, regarding page 

995 in his 1970 article, that Ci0:0 and Ci4:0 do act as 

mild bacterial inhibitors but that d6:0 should not 

have been termed an inhibitor; he also pointed out 

that line 5, column 2, should read "(C8 to C26 )" 

instead of "(Cio to C26 )."] If C12:0 is toxic to certain 

bacteria which contain Ci6:0 as a major component 

of their lipid cells, then the C12:0 to d6:0 ratio might 

be used as an index of the inhibiting effect of lauric 

acid C12:0 upon these bacterial communities. Figure 

6 shows that the Ci2:0 to C16:0 ratio decreases markedly with increasing water depth in an east-to-west 

traverse along the long axis of Choctawhatchee Bay. 

The change with increasing water depth corresponds 

with the combined effect of such geochemical param10

20

30

40 1.0 2.0

C 12:0

3.0 4.0

FIGURE 6. Ci2:o to Ci8:o ratios as a function of depth of water 

for six bottom grab samples collected along an east-to-west 

traverse in Choctawhatchee Bay (fig. 4).

eters as decreasing sunlight reaching the bottom and 

increasing bottom-water salinity resulting from increasing distance from the fresh-water inlet. These 

factors would, in turn, be expected to influence the 

type of organic matter deposited and the kinds of 

bacterial communities existing in the bottom sediments. An additional, unevaluated factor that may 

tend to raise the proportion of Ci6: o in the bottom 

sediment of the estuary is possible sewage pollution 

from Fort Walton Beach, at the west end of the bay. 

J. V. Hunter (1971) reported, in a talk at the 5th 

Rudolfs Conference in 1969, that C16:0 and Cis:i 

(oleic) acids are dominant fatty acids in domestic 

sewages. Ci6: o is relatively most abundant at the west 

end of the bay.

Figure 7 shows the variation of the Ci2:0 to Ci6: o 

ratio with depth of burial for the tidal-marsh, 

estuarine-bayou, and tidal-marsh-river environments. The slopes of the lines for all sets of samples 

are rather similar down to a depth of about 25 

inches: C12 . 0 increases and Ci6:0 decreases in relative 

abundance. This is what would be expected if Ci 2: o 

is an inhibitor for bacterial communities containing 

C16:0 as a major component of their lipid cells.

Three specific examples of what are considered to 

be postdepositional biochemically induced changes in 

the fatty acid distribution have already been described above. Although the samples discussed
FATTY ACIDS, ESTUARINE AND TIDAL-MARSH SEDIMENTS, FLORIDA Bll

10

20

30

40

50

Tidal-marsh-river

environment 

(Econfina River)

Tidal-marsh 

_environment 

(Aucilla River)

0 1.0 2.0

Cl2:0

3.0 4.0

C 16:0

FIGURE 7. Variation, with depth of 

burial, of Ci2:o to Cie:o ratios in sediments from core samples taken from 

tidal-marsh, tidal-marsh-river, and estuarine-bayou environments.

came from different depths and different environments, they have similar C12:0 to C16:0 ratios (fig. 7). 

Moreover, these samples show definite evidence of 

biological attack and have very similar longer to 

shorter chain ratios. In addition, these same samples 

contain relatively small proportions of Ci 2: o to C16: o, 

such as would occur if Ci 2: o were depleted or exhausted as a bacterial toxin. These relationships are 

perhaps best explained in terms of the bacterial 

toxin mechanism proposed by Bradley (1970): C12 -.o 

may act as a bacterial inhibitor, when present in 

sufficient amounts, and thereby reduce the rate of 

bacterial resynthesis of C16:0 within these sediments.

SUMMARY AND CONCLUSIONS

1. The normal even-numbered homologous series of

fatty acids Ci 2:0 through C28 :o were identified in 

sediments from the tidal-marsh, tidal-marshriver, estuarine-bayou, and estuarine environments.

2. The average ratio of relative percentage abundance of longer chain (C20: o through C28:0 ) to 

shorter chain (Ci2:0 through Ci8: o) fatty acids 

was lowest in the estuary, of intermediate 

value in the estuarine bayou and the tidalmarsh river, and highest in the tidal marsh. 

These relations especially a high ratio of 5.25 

in the living rootmat of the tidal marsh 

strongly suggest that the longer chain fatty 

acids (C20: o through C28:0 ) are derived from 

tidal-marsh flora, probably from the plant 

waxes. Marsh flora is obviously an important 

contributor of lipid substances and therefore 

is a potential source material for high-wax 

petroleum accumulations in nearshore brackish-marine rocks.

3. The relative abundance ratios, when plotted as a 

function of depth of burial, were found to vary 

somewhat unsystematically with sediment type 

and amount of plant detritus in the tidalmarsh-river environment, to decrease markedly with depth of burial in the partly exposed 

tidal-marsh environment, and to decrease 

slightly with depth of burial in the estuarinebayou environment.

4. The relative abundance ratio of Ci 2:0 to C16:o 

generally increases at the same rate with depth 

of burial down to about 25 inches for the tidalmarsh, tidal-marsh-river, and estuarine-bayou 

environments. This may mean that, when present in sufficient amounts, Ci2:0 acts as a 

bacterial inhibitor and thereby reduces the 

rate of bacterial resynthesis of C16:0. The 

estuarine bottom sediments show a definite 

decrease in the Ci 2:0 to Ci6: o ratio along an 

east-to-west traverse in Choctawhatchee Bay, 

a decrease which corresponds to an increase in 

depth of water, an increase in bottom-water 

salinity, and an increase in distance from the 

source of inflowing organic matter and sediment of the Choctawhatchee River. These relationships support the bacterial toxin mechanism proposed by Bradley (1970).

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 U.S. GOVERNMENT PRINTING OFFICE: 1971 0 443-513