If you do not need this report after it has served your purpose, please return it to the Geological 

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UNITED STATES DEPARTMENT OF THE INTERIOR 

Harold L. Ickes, Secretary

GEOLOGICAL SURVEY 

W. C. Mendenhall, Director

Professional Paper 186—D

SOME ORGANIC CONSTITUENTS OF A RECENT SEDIMENT 

FROM CHINCOTEAGUE BAY, VIRGINIA

BY

ROGER C. WELLS AND E. THEODORE ERICKSON

Shorter contributions to general geology, 1936

(Pages 69-79)

UNITED STATES

GOVERNMENT PRINTING OFFICE 

WASHINGTON : 1937

For sale by the Superintendent of Documents, Washington, D. C. ----- - Price 10 cents
CONTENTS

Page

Abstract-,--________________________________________________________________________________________________ 69

Introduction________________________________________________________________________________________________ 69

Source of sediment studied_____-_______________________________-___-_______-_______-______-___-__--_-_-__---_- 70

Organic content of the sample.--_-___.__-___-__________-_.._-____-_-_____-___.-__--___----___-_---__--.---_---_-_- 70

Methods of separating the organic matter_______________________________________________________________________ 72

Hot alcohol extract-____-__-___________________________:______________-_____________________-..--_______-- 72

Petroleum ether extract______________________________________________________________________________ 72

Residual alcoholic solution.____________________________________________________________________________ 73

Test of the salts for organic acids_______________________________________________________________________ 74

Treatment with ammonia_________________________________________________________________________________ 75

Action of sodium hydroxide-_____--__-__-______________________-___..-__-_________-__---__--_-------_--_--_ 76

First extraction,______________________________________________________________________________________ 76

Additional extractions._______________________________________________________________________________ 77

Examination of the fatty-acid material________._._______________-______________--__-___-__-__--_---_-__ 77

ILLUSTRATION

Page 

PLATE 15. Map of the Chincoteague Bay region, Accomac County, Va______________________________________ Facing 74

n
SOME ORGANIC CONSTITUENTS OF A RECENT SEDIMENT FROM CHINCOTEAGUE

BAY, VIRGINIA

By ROGER C. WELLS and E. THEODORE ERICKSON

ABSTRACT

This paper is a development of a previous paper by the writers 

which called attention to the possible existence of calcium and 

magnesium salts of organic fatty acids as constituents of sediments and as possible source material in the formation of 

petroleum. Its main purpose, however, is to describe the 

methods of analysis and nature of the products or groups of 

products isolated from a recent sediment.

For the present study portions of sediment weighing nearly 

a kilogram were used for analysis. The material was collected 

under sea water in Chincoteague Bay, Va. This sediment 

contained about 0.7 percent of organic matter, from which a 

number of different substances were isolated by extraction 

with solvents, fractional precipitations, and other methods of 

analysis. The three principal reagents used were alcohol, 

ammonium hydroxide, and sodium hydroxide.

The organic substances or groups of substances found include 

chlorophyll, cholesterol, sulphur, "algin", wax, humic-acid 

material soluble in alcohol, humic-acid material insoluble in 

alcohol, fatty-acid material, pentosans, and acid-soluble organic 

matter. Different fractions of the waxlike material melted at 

89° to 175° C. Different fractions of the free fatty acids eventually obtained ranged in their melting point from below 37° to 

71° C. Several facts indicate that at least some of these fatty 

acids may be present in the sediments as calcium or magnesium 

salts. Among these facts are the tendency of the inorganic bases 

to accompany the fatty acids into the final fractions that were 

separated and the yield of precipitates from somewhat concentrated alcoholic solutions of several of the organic fractions 

when treated with sea water and with alcoholic calcium acetate 

solution.

As the organic content of the sample was only about 0.7 

percent, the percentages of the different organic fractions 

obtained were correspondingly small. The main classes of 

substances found were algin, chlorophyll, sulphur, wax, humicacid complex, fatty-acid material, and acid-soluble organic 

matter. These groups were further subdivided by meltingpoint and other tests. The analytical procedures and results 

are described in systematic detail.

INTRODUCTION

The work of F. W. Clarke l called attention to certain relations among the inorganic constituents contributed to sediments by marine invertebrates, but in 

that study little or no attention was paid to the organic 

constituents. In fact, the samples were purposely 

ignited prior to analysis in order to destroy the organic 

matter. The organic contributions have long been of 

interest to economic geologists because of their bearing 

on the formation of coal and petroleum, and aside from

i Clarke, F. W., and Wheeler, W. C., The inorganic constituents of marine invertebrates: U. S. Geol. Survey Prof. Paper 124,1922.

72045—37

this feature they are of great interest to the geochemist 

on account of their variety and the chemical features 

involved in their progressive changes. Yet the organic 

constituents have been given relatively little study.

The organic constituents may include plant residues 

as well as animal remains, debris of microscopic algae, 

fatty material, the indefinite mixture termed "sapropel"—in short, a great variety of chemical compounds. 

These substances conceivably differ from one sediment 

to another, so that many sedimentary deposits should 

be examined and compared, but on account of the 

time required to make such studies, progress is necessarily slow, and hence the aim of the present paper is 

chiefly to describe in some detail what has been found 

about the nature of the organic matter in a single 

sediment.

In a recent paper by the writers 2 it was suggested 

that fatty acids may find their way into marine sediments in the form of insoluble calcium and magnesium 

salts. That viewpoint has been kept in mind in the 

present study. The experimental work here described 

is almost entirely that of the junior author, but 

responsibility for certain details of the investigation 

and for the conclusions is shared by the senior author.

Twenhofel 3 has summarized such information as is 

available on the more general chemical composition of 

sediments. The content of organic matter in sediments has also been rather fully studied by Trask, 

Hammar, and Wu,4 but in attempting to cover a verylarge field they were obliged to limit their work for 

the most part to determinations of carbon and nitrogen, 

supplemented by the use of the customary solvents for 

organic matter. A beginning was made in studying 

the nature of the organic matter in some samples, but 

much remained to be done, and it seemed well worth 

while to the writers to make a more extended analysis 

of the organic matter in a single sediment. They are 

greatly indebted to Mr. Trask for helpful suggestions 

in the preparation of this paper.

2 Wells, R. C., and Erickson, E. T., The analysis and composition of fatty material produced by the decomposition of herring in sea water: Am. Chem. Soe. 

Jour., vol. 55, pp. 338-341, 1933.

s Twenhofel, W. EL, Treatise on sedimentation, 2d ed., eh. 1-4, Baltimore, Williams 

& Wilkins Co., 1932.

4 Trask, P. D., Hammar, H. E., and Wu, C. C., Origin and environment of source 

sediments of petroleum, Houston, Tex., Gulf Publishing Co., 1932.

69
70 SHORTER CONTRIBUTIONS TO GENERAL GEOLOGY, 1936

David White 5 gives a concise summary of the 

present knowledge of the chemical changes in sediments. He points out that the carbonaceous material 

originally consists principally of the residues of plants 

or animals, more especially of plants. The early 

chemical changes are largely covered by the single 

word "decomposition", including biochemical decomposition, and the later changes are referred for the 

most part to those observable in the solid residues, 

the coals.

As a matter of fact, sapropel may also contain a 

high percentage of coprolitic matter, ejected or nonassimilable by both organisms and bacteria, which 

tends to accumulate because it is nonassimilable. 

Just what kinds of compounds may be so classed under 

marine conditions is not well known. Possibly waxlike substances, carbohydrates, fats, fatty acids, and 

soaps are the principal types. Anaerobic bacteria 

tend in the earlier stage of their activity to develop 

acidity, but where protein material is available the 

ammonia generated by its decomposition tends to 

produce an alkaline environment, at least temporarily, 

and sea water itself has an alkaline reaction. Some 

bacteria and lower organisms are poisoned by the 

higher fatty acids and soaps. Other bacteria convert 

different fatty acids into methane rather than into 

the expected higher hydrocarbons.6 On the other hand, 

some bacteria and molds produce fats.7 Hammar 8 concludes from an extensive survey of the literature that 

there is little or no evidence that hydrocarbons higher 

than methane are formed from other organic substances 

by bacteria.

These conflicting statements leave some doubt as to 

the fate of fatty acids from anaerobic bacterial attack, 

but in any case there will still remain the humus or 

residue. In this connection Waksman 9 says: "The 

marine humus, just as the soil humus, is formed by 

similar micro-organisms in a very similar manner", 

but certain differences in chemical nature from land 

humus are accounted for by the fact that marine 

residues, from which all or part of the humus is formed, 

are different in chemical composition from the land 

residues from which soil humus is formed. Thus, land 

vascular plants have a notable lignin content, which 

is lacking in algal material. For the problem here 

considered the principal differences in the marine environment are the alkaline reaction of the water and 

the presence of calcium and magnesium salts. The

' White, David, in Twenhofel, W. H., op. cit., p. 415; The origin of petroleum, in 

Petroleum investigation: 73d Cong. (recess), Hearings on H. Res. 441, pt. 2, pp. 

898-906, 1934.

6 Thayer, L. H., Bacterial genesis of hydrocarbons from fatty acids: Am. Assoc. 

Petroleum Geologists Bull., vol. 15, pp. 441-453, 1931.

7 Ward, G. E., Lockwood, L. B., and May, O. E., Production of fat from glucose 

by molds: Ind. and Eng. Chemistry, vol. 27, pp. 318-322, 1935.

8 Hammar, H. E., Relation of micro-organisms to generation of petroleum: Problems of petroleum geology (Sidney Powers memorial volume), pp. 35-50, Am. Assoc. 

Petroleum Geologists, 1934.

9 Waksman, S. A., The role of bacteria in the cycle of life in the sea: Sci. Monthly, 

vol. 38, pp. 35-49, 1934.

present study gives some indication of what kinds of 

organic matter may survive at an early stage of 

sedimentation.

SOURCE OF SEDIMENT STUDIED

The sample of sediment used in the present investigation was collected by E. T. Erickson in September 

1932, at a locality in Chincoteague Bay, Va., about 

half a mile northwest of Killick Shoal Lighthouse, at 

the point marked "X" in plate 15. Here the bottom 

of the bay was approximately level and was just 

reached with an ordinary long-handled shovel from a 

small boat. The nearest land was the eastern member 

of a group of islands in Chincoteague Channel, about 

a mile south. Dr. Paul Bartsch, of the United States 

National Museum, to whom acknowledgment is gratefully made, suggested this locality on account of its 

marine life and convenient accessibility from Washington. Acknowledgment is also made to Mr. Archie 

Bradford, of Chincoteague Island, for assistance in collecting the sample and other materials studied. The 

water is essentially coastal sea water in a marginal 

lagoon or bay. The land nearby is covered with saltmarsh grass, and the shores are strewn with abundant 

masses of algae. In the water or on the bottom may 

be found fishes, sponges, and oysters. But K. E. 

Loliman, of the Geological Survey, found no Foraminifera or diatoms in the sample collected, which is 

mainly quartz sand with some mud. Dr. Bartsch 

suggests that the absence of diatoms may be due to 

their effective removal from the water by oysters, 

whose culture has increased in the bay in recent years.

The sample was dark gray when wet, lighter gray 

when dried. Its inorganic chemical composition is 

shown in table 1.

TABLE 1.—Analysis of sediment from Chincoteague Bay, Va.

[E. T. Erickson, analyst]

SiO2 -----~---~--- 76.32

Fe2O3 -___-_---_--- 1.08

A12O3—-___-___ 10.69

TiO2 - 

P205 _. 

CaO_ 

MgO_ 

Na2O. 

K2O_.

.46

.07

1.46

.77

1.65

1.90

NaCl__.____.__-._

MnO_.__________

SO3 ____________ 

Loss at 105°.________

Further loss on ignition_____________

0.88

.02

.31

1.55

3.34

Total. ________ 100.50

ORGANIC CONTENT OF THE SAMPLE

The organic content of the sample, other than carbonate, was small—approximately 0.7 percent, based 

on the total products extracted. The material dried 

on the steam bath gave 0.41 percent of carbon as the 

average of three determinations (0.38, 0.45, 0.40), and 

0.0755 percent of nitrogen as the average of two determinations (0.076 and 0.075). Engler 10 has expressed 

the view that little nitrogen is to be expected in sedi10 Engler, C., in Potonie, H., Zur Frage nach dem TIr-Materialien der Petrolea: 

K. preuss. geol. Landesanstalt Jahrb., Band 25, p. 342,1904.
SOME ORGANIC CONSTITUENTS OF A RECENT SEDIMENT 71

mentary sapropelic matter, as the nitrogen would be 

removed by biochemical processes before or during 

deposition. These are the first changes affecting the 

chemical composition of the sapropel. Nitrogenous 

compounds tend to move in a cycle rather than to 

become fixed in sediment, but according to Trask the 

nitrogen in most sediments ranges from one-seventh 

to one-eighteenth of the carbon. 11 In living matter 

the nitrogen-carbon ratio has a wide range, depending 

on the nature of the material.

The main organic substances or classes of substances 

separated from the sediment of Chincoteague Bay are 

as follows:

Percentage of organic substances in sediment of Chincoteague Bay

Algin_______________________________ 0. 037

ChlorophylL___________________________ . 003

Sulphur,-__---_--_____________________ . 006

Wax__________________________________ . 023

Humic-acid complex insoluble in alcohol

after isolation______________________ .075

Humic-acid complex soluble in alcohol after

isolation_____________________________ . 116

Fatty-acid material.-___________________ . 034

Acid-soluble organic matter______________ . 448

It should not be thought that these substances necessarily exist as such in the free state in the sediments. 

There is clear evidence that some of them do not, although some may. One of the most difficult parts of 

the problem is to determine in what form they are 

actually present.

It seems clear that sulphur is present in the free state, 

though some may also be combined. Chlorophyll is 

probably present in the free state and in residues of 

plant tissue. The chemical formula of alpha-chlorophyll is C55H72O5N4Mg, with a carbon-nitrogen ratio 

of 11.8. This complex molecule is decomposed by 

treatment with either strong acids or alkalies and yields 

methyl alcohol and phytyl alcohol, C2oH4oO, a primary 

unsaturated, monohydric alcohol, but it apparently 

dissolved directly without decomposition in the alcohol 

with which the organic matter was extracted from the 

sediment. The "algin" appears to be a colloidal complex of a hygroscopic nature. The writers believe that 

some of the "humic acids" and probably also some of 

the fatty acids are present as calcium and magnesium 

salts.

The waxes probably occur in the sediment in the free 

state; chemically these substances are salts or esters 

of the higher alcohols and aeids. Kramer and Spilker 12 

found that "sea-weed wax" obtained from algae appeared to consist of esters of alcohols containing 20 to 

22 atoms of carbon united with arachidic, behenic, and 

lignoceric acids, and that it had a fairly low melting 

point. The wax from diatoms melted at 50° to 70°

u Trask, P. D., Hammar, H. E., and Wu, C. C., op. cit., p. 22. 

12 Kramer, Q., and Spilker, A., Das Algenwaehs und sein Zusammenhang mit dem 

Erdol: Deutsche chem. Gesell. Ber., Jahrg. 35, p. 1212,1902.

C.13 Waxes extracted from peat melt much higher. 14 

Wax from the Chincoteague Bay sediment ranged in 

melting point from 25° to 90°, indicating a great variety 

of compounds. The survival of waxes in the sediments 

suggests that they are not assimilated by animals, 

though no direct evidence on this point is available. 

They may possibly even be built up by micro-organisms.

Extraction of the sediment with alcohol having removed "algin", chlorophyll, sulphur, wax, and some 

oily matter, the material was next treated either with 

ammonia or with dilute caustic soda solution. This 

procedure raises the question of the nature of the action 

of these reagents. It is well known that they bring 

a large proportion of organic matter into solution, but 

do they act simply as solvents and as hydrolyzing agents 

or by base exchange, forming salts with weak acids and 

compounds carrying exchangeable hydrogen? It seems 

likely that calcium and magnesium salts of organic acids 

may be present in the sediments rather than the free 

acids, and therefore the action of the alkalies is probably 

in part of the nature of a base exchange. If it is desired 

to minimize decomposition of the higher and complex 

molecules during the extraction, ammonia is preferable 

to the caustic alkalies on account of its milder action 

on the organic compounds.

Schreiner and Shorey 15 emphasize the fact that the 

organic matter of soils is reactive to the inorganic 

matter, and the same must be even more true of sediments deposited in sea water, which contain calcium 

and magnesium ions available to form insoluble compounds with such acids. In other words, the organic 

"acids" may be present in part as inorganic salts, 

besides existing as esters and adsorption complexes. 

Although this is not a new idea, it has received little 

emphasis heretofore.

At least two lines of evidence offer support for the 

idea. First, when the organic matter is extracted and 

concentrated in certain solvents, as described in the 

following pages, an inorganic part containing SiO2, 

K2O3 , MgO, CaO, and a few other oxides tends to 

accompany the organic matter. Second, when the 

organic acids are set free with hydrochloric acid, extracted with benzene, then with alcohol after evaporating the benzene, the alcoholic solution gives a precipitate with sea water. A precipitate may also be 

obtained, if fatty acids are initially present, with an 

alcoholic solution of calcium acetate—a test proposed 

by Mr. Erickson. Such a solution is easily made by 

shaking at intervals during 15 minutes about 1 gram 

of. calcium acetate with 55 milliliters of 95-percent 

alcohol and filtering, and it appears to be a convenient 

reagent for some purposes. That the reagent indicates

13 Kramer, G., and Spilker, A., Das Wachs der Bacillariaceen und sein ZusammenLang mit dem Erdol: Deutsche chem. Gesell. Ber., Jahrg. 32, Band 3, p. 2940, 1899.

14 Lewkowitsch, J., Chemical technology and analysis of oils, fats, and waxes, 

5th ed., vol. 3, p. 282, 1915.

15 Schreiner, O., and Shorey, E. C., Chemical nature of soil organic matter: U. S. 

Bur. Soils Bull. 74, 1910.
72 SHORTER CONTRIBUTIONS TO GENERAL GEOLOGY, 1936

the presence of fatty acids only has not been shown. 

The facts so far established are simply that "organic 

acids" are present in the sediment in small quantities 

and may be shown to give calcium precipitates with 

the reagent, or sea water, and among the acids so far 

identified are members of the paraffin series generally 

termed the "fatty acids."

Nitrogen was proved to be present in the humic-acid 

groups, though partly lost in the extraction. It is 

probably present largely as protein, but just what kind 

of protein has not yet been determined.

METHODS OF SEPARATING THE ORGANIC MATTER

The general scheme of analysis and separation of the 

different groups of constituents is shown in tables 2

and 5. In these tables the following abbreviations are 

used: R, residue; F, filtrate; P, precipitate; E, extract; 

S, solution. The figures in the tables refer to weights 

in grams of the different fractions obtained. The 

scheme is partly modeled on the work of Oden,lti partly 

on that of Schreiner and Shorey 17 and on other work. 

These methods are the best so far developed for separating the organic matter into classes which can be tested 

for individual substances. The time has not yet arrived when some specific test can be made for each 

substance or even for each class of substances. The 

desired knowledge can be obtained only by successive 

approximations through a series of steps. The original 

samples were dried on the steam bath before weighing 

out portions for study.

TABLE 2.—Outline of method of analysis

Extract with hot alcohol.

Ri. Heat with 600 ml of dilute NH4OH. Filter.

Rg. Repeat the extraction 

and finally 

discard 

residue.

F9 . Evaporate slowly to 150 ml. Filter.

Rio. "Re- versed" 

precipitate, 

0.8641.

FIO. Add 25 ml of acetic acid and filter.

P4 . Treat with 

hot alcohol.

Ru . Insoluble, 

1.462.

Fu. Soluble, 

0.390.

Fn . Treat with 

hot alcohol.

Ri2 . Insoluble, 

6.671.

Pi,. Soluble, 

1.531.

FI. Concentrate and filter off the insoluble inorganic salts.

F5 . Extract with petroleum ether.

Si. Residual solution. 

Extract with benzene.

R3 . "Algin'S 

0.300. 

Extract with 

absolute 

alcohol. 

R13, 0.026. 

FM, 0.1509.

Ej, 0.055.

F6 . Petroleum ether 

extract. Extract 

with alcohol, 

0.333.

R6 . See 

table 3. 

Wax, 

0.190; 

sulphur, 

0.051.

F7 - Chlorophyll, 

etc., 

0.024. 

Oily 

matter, 

0.068.

R4 . Salts, 

3.76.

HOT AICOHOL EXTRACT

A portion of the sample weighing 811 grams was 

extracted three times with 95 percent ethyl alcohol on 

the steam bath in a covered flask, using about 600 

milliliters of alcohol each time. The duration of the 

heating varied from several days for the first extraction 

to overnight for the last one. While hot, each alcoholic 

solution was filtered. The first filtrate was noticeably 

green, the last practically colorless. This procedure 

left residue Rt , which was reserved for further treatment.

The combined alcoholic extracts (Fx ) were evaporated 

to 50 milliliters and filtered. The insoluble material 

thus obtained was heated with successive small quantities of alcohol and filtered off until it was practically 

white and nearly free from organic matter; it then 

weighed 3.76 grams (R4).

The combined alcoholic nitrate (F5), evaporated to 

about 50 milliliters, was then placed in a separatory 

funnel and extracted several times with light petroleum 

ether. The first ether extract had a strong green color; 

the last was only slightly colored. Some green matter

also remained in the residual alcoholic solution, thus 

showing at least two kinds of green pigment. Ordinary 

chlorophyll is soluble in light petroleum ether. The 

total ether extract weighed 0.333 gram.

PETROUEUM ETHER EXTRACT

The ether extract (F6 ), after evaporation of the 

solvent, was treated with small quantities of alcohol 

until little coloring matter remained. Waxy matter 

tended to remain in the insoluble part (R6 ). The 

treatment was continued until from the soluble portion 

a final green viscous residue was obtained which would 

all dissolve in about 1 miliiliter of alcohol (F7).

On treating the residue from evaporation of F7 with 

still less alcohol the green portion was distinctly more 

soluble than the remainder. In this solution cholesterol 

was identified by the digitonin reaction, 18 but the

'« OdSn, Sven, Die Huminsauren; chemische, physikalische und bodenkundliche 

Forschungen: Kolloid-chemisehe Beihefte, Band 11, pp. 76-260, 1919.

17 Schreiner, O., and Shorey, E. C., op. cit.

18 Holde, D., The examination of hydrocarbon oils and saponifiable fats and waxes, 

tr. by E. Mueller, p, 350, New York, John Wiley & Sons, 1922.
SOME ORGANIC CONSTITUENTS OF A RECENT SEDIMENT 73

quantity was too small for determination or further 

study. Chlorophyll was definitely identified, aside 

from its color, by the copper acetate test. 19

The rest of F7 was then saponified with alcoholic 

potash solution. A little lead acetate solution was then 

added, which resulted in precipitation of the lead salts 

of the organic acids. The lead precipitate was filtered 

off, washed with hot water, dried, and decomposed with 

warm 20 percent hydrochloric acid, and the resulting 

mixture was extracted with benzene. The benzene 

solution, when separated in a separately funnel, 

yielded 0.039 gram of oil-like matter on evaporation. 

This fraction may represent acids derived from algal 

oils. The remaining acid solution on evaporation to 

dryness and extraction with alcohol yielded 0.029 gram 

of brown amber-colored material that was fairly solid at

room temperature. These acids were not fully studied. 

The filtrate from the lead salts, which may have contained alcohols, was colorless. It was not studied 

further.

The residue of wax (R6 ) was fractionated with ether 

to separate sulphur. Repeated slow evaporations of 

the ether solution yielded small crystals of sulphur, 

which were picked out with a needle, with the aid of 

a hand lens, giving in all 0.051 gram of sulphur.

The wax was then subjected to a series of fractionations in different solvents, with tests of each fraction, 

as shown in table 3. The first fraction of wax represents 

the portion of R6 that is relatively insoluble in alcohol 

but more soluble than in benzene, and similarly for the 

succeeding fractions.

TABLE 3.—Results of fractionation of the waxlike material (R6 ) after separation from sulphur

soluble in alcohol.

soluble in warm ether.

insoluble in cold ether.

fractions from cold ether. 

Do. __________

Do__ _____

Do____. _______ _

Residue _

Total_____._____

Fraction 

(gram)

0. 031

.021

.016

.026

.011

.008

094

.053

. 190

Melting point (°C.)

89_________________

70-81

70±___.__ ___ ___ _

Softened below 100°

C. but not clearly 

melted till 175° C. 

-____do____. ________

50-60______________

25° C.

Lieberman's test

color. 

__.__do___-____-__---_

_____do____ ___ ______

_____do________. ______

-_-__do____.__-_______

_____do________ ____ _

stronger color results. More reddishgreenish than reddish.

Reactivity with alcoholic lead acetate i

Small- — — __

——do—..—

_____do_______

____ _do_-____-

_____do_.__.__

_____do______-

———do————

Properties

Mixture. Some crystalline material. 

Light-colored and waxlike.

Do.

Do.

Strong tendency to threadlike crystals. Practically white. 

Similar to above.

Softer, waxlike. A little

sulphur present. 

Softer, waxlike, but contains some yellowishgreen matter. A little 

sulphur present.

1 Test carried out in a similar way with palmitic acid gave a definite precipitate.

The various fractions of wax were tested for cholesterol by the Lieberman test 20 and for fatty acids with 

alcoholic lead acetate, but only small quantities were 

found. The results of these tests are shown in the i 

fourth and fifth columns of table 3. A wide range of 

melting point of the waxes is shown. They were not 

individually identified.

Fractions found in petroleum ether extract

FT. Organic acids insoluble in benzene but

F7 . Chlorophyll fraction (by difference) ____ 

TotaL ____ _ .. ____ _____ _

Gram

0. 190 

.051 

.039

. 029 

. 024

. 333

Percent of 

sample

0.023 

.006 

.005

.004 

.003

. 041

18 Onslow, M. W., Practical plant biochemistry, p. 32, Cambridge Uuiv, Press, 

1920. 

MJSolde, D., op. cit., p. 519.

RESIDUAL ALCOHOLIC SOLUTTON

The alcoholic solution (SJ remaining in the separatory funnel after treatment with light petroleum ether 

still contained some green material. The mixture was 

extracted with benzene, yielding two layers; the benzene solution on evaporation left a green residue, E2 , 

weighing 0.055 gram, which was partly crystalline. 

On account of its small weight this residue was not 

studied further.

On evaporating the remaining alcohol to a small 

volume, a further small quantity of inorganic salt was 

precipitated, which was added to R4- The remaining 

alcoholic solution, which contained considerable organic matter, was evaporated, and yielded approximately 0.30 gram of olive-gray organic matter (R3 ) 

that appeared either dry or moist according to the 

humidity of the air. This material was thought to 

be an inorganic salt of an "algin" component. It 

appeared to be a complex mixture of carbohydrates 

and other organic matter and some inorganic matter.
74 SHORTER CONTRIBUTIONS TO GENERAL GEOLOGY, 1936

When heated directly in a test tube it yielded some 

volatile tarry or oily matter and left a carbonized 

residue. Similar material was later found in the 

alkali extracts. The dried residue was extracted with 

small volumes of absolute alcohol and yielded 0.0264 

gram of insoluble material (Ri3) and 0.1509 gram of 

soluble material (Fu). These two parts were studied 

as thoroughly as the rather small quantities would 

permit.

• The insoluble part (Ri3) was too small to study very 

thoroughly, but as tests showed that considerable 

inorganic matter accompanied the organic, a partial 

analysis was made, with the following results:

Results of partial analysis of inorganic matter in RW

SiO2 ._ ___ —— _ —— _ ———————— _

R*Oi

MeO

CaO_-_ — —— - - - - -----------

K20___- —— ——— — —— — —— — —

Na_O_- _ — __ — —— — _ —— _ — _ — _

S03 ---- — -------------------------

Total.. ______________________

Percent of 

fraction

3.7

7.0

4. 7

4. 2

1.9

11. 4

17.9

44.0

94.8

Percent of 

sediment

0 0001

0002

0001

0001

0001

0004

0006

0014

.0030

On digesting a portion with hydrochloric acid, 

evaporating, and extracting with benzene, a soft material resembling a fafcty acid was obtamed. This 

material, when dissolved in alcohol, gave a fairly 

definite precipitate with a solution of calcium acetate 

in alcohol. This precipitate appears to be one of the 

fractions hi which part of the calcium and magnesium 

salts of the organic acids became concentrated.

The part soluble in absolute alcohol (Fi4), which 

weighed 0.1509 gram, gave the following results:

Results of partial analysis of inorganic matter in FU

R-zCK

MgO__—— ———_-_ — __ — -_ —— __-_._

CaO--——— _ —— —— ——— — — -_ — -_

Loss on ignition_____ _ __ ____ _______

Total, _________________ _

Percent of 

fraction

5. 4

1.3

2.7

83.3

92.7

Percent of 

sediment

0. 0010

. 00024

.0005

.0155

.0194

This fraction was only slightly soluble hi benzene, 

yielding a minute quantity of free sulphur and waxlike 

material. A small quantity of the dried material, on 

testing with dilute sodium hydroxide and iodine solution at room temperature, soon gave a persistent odor 

of iodoform, like that given by levulinic acid. It is 

thought that this acid or some analogous acid was 

present in this fraction. Similar material might possibly have been found in portions E2 , R6> and F7, if tests 

had been made.

The same lot of the sediment was heated a fourth time 

with alcohol, and the alcohol was filtered off hot and 

evaporated, yielding a further small quantity of inorganic salts and some organic matter. It is unnecessary, however, to give details of these tests, as they 

yielded results essentially similar to those already 

described, except that the quantities of material 

obtained were smaller. Unfortunately lack of time has 

prevented the determination of the carbon-nitrogen 

ratios in the different fractions. Such determinations, 

as Mr. Trask has pointed out: in conversation with the 

writers, would be very desirable for comparison with 

his results and would help to throw light on the nature 

of the organic material. Some nitrogen compounds 

were indeed obtained in the extractions with sodium 

hydroxide described later, but it was felt that this 

treatment also caused a partial loss of the nitrogen.

TEST OF THE SALTS FOR ORGANIC ACIDS

If calcium salts of the fatty acids, for example, were 

present in the sample, some of them would probably 

have been dissolved by the large volume of solvent 

alcohol used, but they would also probably have tended 

to reprecipitate along with the inorganic salts as the 

alcohol was evaporated, as the solubility of such salts 

is generally low. Few exact figures on their solubility 

are available. Beilstein 21 gives the solubility of 

calcium palmitate in alcohol at 20° C. as 0.0103 part 

per hundred. K. J. Murata, of the Geological Survey 

laboratory, in studies now in progress, finds 0.0074 

part of calcium mucate (CaC6H8O8.4H2O) per hundred 

at 25° C.

Two grams of the inorganic salts (R4) separated by 

concentration of the original solvent alcohol was heated 

with 55 milliliters of 10 percent hydrochloric acid and, 

on cooling, extracted with benzene. Evaporation of 

the filtered benzene gave a somewhat colored waxlike 

residue weighing 0.0059 gram. This was treated with 

2 milliliters of alcohol, and 0.2 milliliter of the calcium 

acetate reagent was added to the filtered solution. A 

precipitate resulted about equal in bulk to that 

obtained from 1 milligram of palmitic acid. Hence, 

the quantity of calcium soaps extracted by the alcohol 

was insignificant compared with the fatty acids found 

later on treatment with caustic soda (EO. The writers 

accordingly conclude that the calcium soaps are held 

hi the sediment in an adsorption complex, from which 

they are not removed by such a solvent as alcohol but 

are easily brought into solution by metathesis with the 

strong alkali.

A recent paper by Duncan 22 calls attention to the 

fact that calcium and magnesium salts of certain 

sulphonated alcohol esters are easily or moderately 

soluble in water, and hence esters of this type may 

probably be excluded from consideration as constituents

21 Beilstein, F., Handbuch der organischen Chemie, 3« Aufl., Band 1, p. 443,1893.

22 Duncan, B. A., The new detergents: Ind. and Eng. Chemistry, vol. 26, pp. 24-26, 

1934.
C. S. GEOLOGICAL STJBVEY PBOFESSIONAL PAPER 186 PLATE 15

'• 3 •' /a AncMorage'- if . •'

Base from U.S. Coast and i 3 Miles

Geodetic Survey charts 1-1 >-i t-i r-i i—ii

MAP OF THE CHINCOTEAGUE BAY REGION, ACCOMAC COUNTY, VA.

SOME ORGANIC CONSTITUENTS OF A RECENT SEDIMENT 75

of sediments formed in sea water, unless they also 

should be held in an adsorption complex.

TREATMENT WITH AMMONIA

The residue KI, after extraction with alcohol as 

previously described, was treated five times at about 

97° C. with dilute ammonia, in 600-milliliter portions 

in flasks immersed in a steam bath. Each portion 

after filtration was slowly evaporated to about 150 

milliliters. This treatment resulted in a "reversal" or 

reprecipitation of dissolved material (Rio). Absorption 

of carbon dioxide from the air may have helped to cause 

the reprecipitation. The total "reversed" precipitate 

amounted in all to 0.8641 gram, or 0.31 percent of the 

sample (811 grams).

The dark-brown ammoniacal filtrate was found to 

yield a precipitate with sea water. For example, 2 

milliliters of the filtrate, on standing 10 days with an 

excess of sea water, lost its amber-brown color, and a 

flocculent precipitate appeared in the bottom of the 

solution.

Table 4 summarizes the results of the extractions with 

ammonia. The third column gives the weights of the 

"reversed" precipitate (Ri0 ). The next two columns 

give the material precipitated on neutralization with 

25 milliliters of acetic acid, expressed as material 

insoluble and material soluble in hot alcohol. The last 

two columns give similar figures for the material remaining in the acetic-acid solution. Extracts 2 and 3 

were combined to save time. The terms "1st" and 

"2d" under "reversed" precipitate refer to successive 

crops.

TABLE 4.—Results of extraction with ammonia (in grams)

No.

1 _________

2,3_______

4__. ______

5__ ____ _

Total

Strength of ammonia (percent)

10

10

15 

1 25

"Reversed" precipitate (Rio)

/0.5264 (1st) 

I .0378 (2d) 

/ .1583 (1st) 

X .0526 (2d) 

.0890

.8641

Precipitated by 

acetic acid (P^

Insoluble in 

alcohol 

(Rn)

}o. 823

} . 416 

.223

1. 462

Soluble in alcohol 

(Fii)

0. 269

.090 

.031

.390

Remainder (Fn)

Insoluble in 

alcohol 

(Rn)

5. 082

1.001

.588

6. 671

Soluble in alcohol 

(F13)

1. Oil

.404 

. 116

1.531

i The total extract of 0.6414 gram from the fifth treatment was not separated further.

All these fractions contained organic matter, ranging 

from perhaps 10 to 94 percent, but some also contained 

considerable inorganic matter. The inorganic matter 

appeared to be more than would be expected in products 

of ordinary solubility and must have included some 

organic compounds, or else the excessive solubility 

must have been due to the presence of organic matter. 

Silica was high in some of these extracts, also sulphate.

The two largest portions of the "reversed" precipitate noted in table 4 (0.6847 gram) were partially 

analyzed, with the following results:

Partial analysis of greater part of "reversed" precipitate

Si02

R2 03 __ ___ ___________________ ________

MgO— _ ___________ _________ _ _

CaO_ — _----_----------------_--------

Total.. ___ _____ ___ ___ _

After warming with a little 5 percent HC1, 

evaporating, and extracting with alcoholPercent of 

fraction

48. 9

4.4

.8

4.0

33.5

91. 6

3.2

24.8 

8. 3

Percent of 

sediment

0. 0413

.0037

.0007

.0034

. 0282

.0773

.0027

.0209 

.0070

The material soluble in alcohol after treatment with 

hydrochloric acid gave a slight precipitate with alcoholic 

calcium acetate solution. The results were somewhat 

better if the alcoholic extract was first concentrated to 

a smaller volume. Blank tests with reagents gave no 

precipitate.

Similar tests were made of the remainder of the 

"reversed" precipitate (0.1794 gram) with the following 

results:

Partial analysis of remainder of "reversed" precipitate

MgO_____..

CaO___-_-_--. 

Loss on ignition.

Total..________________.

Soluble in alcohol______________________

After warming with a little 5 percent HC1,

evaporating, and extracting with alcohol.

Ammonia-soluble material in residue______.

Percent of 

fraction

36.4

14. 6

5.4

3.4

39.4

99. 2 

1.5

5. 9 

18.6

Percent of 

sediment

0. 0080

. 0031

.0012

.0008

.0087

. 0218

.0003

.0013

.0041

The calcium acetate test, when applied to the alcohol 

extracts, gave results similar to those obtained with the 

larger fractions. The alcoholic solutions evidently 

contained other organic matter, in addition to fatty 

acids. They gave brownish-white precipitates with 

alcoholic lead acetate. The final ammoniacal extracts 

noted above were dark, but were not studied further.

The fraction precipitated by acetic acid and insoluble 

in alcohol (Kn) gave the following results:

Partial analysis of fraction Rn

SiO,_. ....... _—_ — ___——-— — -_

E203 - __ - ___ -_- _______ - __ -- _

MffO

CaO__-_________-___-__._____--___-___

Total.. __________________

Percent of 

fraction

1.2

1.2

Trace

0.4

91.6

94.4

Percent of 

sediment

0. 0022

.0022

.0000

.0007

. 1650

. 1701
76 SHORTER CONTRIBUTIONS TO GENERAL GEOLOGY, 1936

When examined by the method of Tollens and 

others,23 this material appeared to contain pentosans, 

as it yielded 2.6 percent of methyl pentose and 2.8 

percent of pentose. It probably also contained socalled "humic acids."

The fraction precipitated by acetic acid and soluble 

in alcohol (F12 ) gave the following results:

Partial analysis of fraction F\t,

RaO8 ~ — —— —— —— — — — — — —— - --------

MgO—_____ — __--- — -- — — — — - — -

CaO__ — — — — — — — — — — — — — —

Total.. _. _ _ _ __ _._ _ __

Percent of 

fraction

0. 9

. 3

1. 7

94. 5

97.4

Percent of 

sediment

0. 0004

. 0001

. 0008

.0453

. 0466

Fatty acids were definitely obtained from this material by the procedure previously described. The material was low in inorganic matter. It probably also 

contained pentosans and alcohol-soluble "humic acids."

The remainder of the acetic-acid solution gave 6.671 

grams of material insoluble in alcohol (Ri2 ). It was 

analyzed with the following results:

Analysis of fraction J?i2

SiO2 -__ -------------------------------

R203 ---------------------------- ___ --

SO3 ___-----____--_--__-_-_--_--________

Cl___-__--__.______. ___________________

MgO— _ _____________________________

CaO_ __________________________________

Na2O_ -____-_--_-________--_-_--_-__-_-

K2O__ _________________________________

Total__ . ___ ____ ___ __

Percent of 

fraction

0.5

.3

22. 2

. 5

. 1

. 1

19. 0

3. 3

51.0

97. 0

Percent of 

sediment

0 0042

0025

1826

0042

0008

0008

1563

0271

41Q*i

. 7980

Methyl pentose was estimated at 2.1 percent in this 

fraction and pentose at 4.2 percent. The fraction, 

though insoluble in alcohol, is soluble in water and is 

the dominant fraction of organic matter in the sediment. Some sodium sulphate appears to be present. 

Some marine algae gathered at the time the sediment 

was collected gave similarly from the dried material 

5.9 percent of methyl pentose and 3.7 percent of pentose—a result which strongly suggests that marine 

algae are a prominent source of organic matter in the 

sediment. The material in fraction R12 forms a 

precipitate with sea water more slowly than the fraction precipitated by acetic acid (F12 ). In addition to 

the pentoses some acids are probably present, though 

they were not identified. In a similar fraction from

s» Mayer, Willy, and Tollens, B., Ueber die Fnkose und die Bestimmung der 

methyl Pentosane in Naturprodukten: Jour. Landwirtschaft, Band 55, pp. 261-271, 

1907.

soil Shorey 24 found saccharic acid ((CHOH)4 (COOH) 2 ), 

acrylic acid (CH2 :CHCOOH), and some amino acids. 

The material of the last fraction (Fi3 ) was ambercolored and somewhat sirupy in appearance. That it 

contained some carbohydrate was shown by the 

Molisch alpha-naphthol test.

ACTION OF SODIUM HYDROXIDE

FIRST EXTRACTION

As an alternative to the treatment with ammonia 

use was also made of the more drastic reagent sodium 

hydroxide. The procedure is outlined in table 5. A 

separate portion of the original sample weighing 863 

grams was extracted with alcohol, as previously described, but beginning with the residue R! this material 

was next heated for a week with about 750 milliliters 

of 2 percent sodium hydroxide solution in a flask 

immersed in a steam bath. The neck of the flask 

protruding from the steam bath was covered with a 

watch glass to prevent evaporation. The hot solution was filtered off, the residue was washed briefly 

with water, and the filtrate (F2 ), which was dark from 

organic matter, was made slightly acid with hydrochloric acid. The resulting flocculent precipitate (Pt) 

was filtered off, washed briefly with water, and transferred while moist to 95 percent alcohol. This mixture 

was boiled and filtered, thus yielding Oden's "alcoholinsoluble" humic-acid complex (P2). This material 

was dried and weighed 0.312 gram. More was obtained 

from further treatments, as described below, and the 

weights given in table 5 represent the totals of four 

extractions (also summarized in table 6).

The alcoholic filtrate of considerable volume from 

P2 (F4), which was also dark from organic matter, was 

treated with an excess of alcoholic lead acetate, heated 

on the steam bath, and filtered, yielding the insoluble 

lead salts (P3 ) and a soluble portion (F7 ).

The lead salts insoluble in alcohol (t^) were digested 

with 20 percent hydrochloric acid, the acid slowly 

evaporated, and the residue extracted with alcohol. 

The alcoholic solution was transferred to a porcelain 

dish and evaporated; the first residue weighed 0.280 

gram, and succeeding portions similarly treated gave 

a total yield of 1.007 grams (R8 ). This material, 

which was not very soluble in benzene, is the analytical 

equivalent of Oden's "hymetanelansaure", or alcoholsoluble humic acid.

The soluble portion (F7 ) was evaporated, digested 

with 20 percent hydrochloric acid, and extracted with 

benzene. This procedure left a residue (R7 ). The 

extract (E^ contained mainly solid fatty-acid material, 

the first yield weighing 0.0455 gram and the total 

0.293 gram. Its treatment is described more fully 

below.

u Shorey, E. C., Some organic acid constituents: U. S. Dept. Agr., Bur. Soils, 

Bull. 88, p. 11,1913.
SOME ORGANIC CONSTITUENTS OF A RECENT SEDIMENT 77

TABLE 5.—Scheme of analysis by using NaOH on residue (Ri) extracted with alcohol (table 2}

[ Results in grams]

Heat with NaOH 750-ml solution and filter.

R2 . Discard.

F2 . Add HC1. Filter.

PI. Add to hot alcohol.

P2 . Insoluble, 

0.648. F4 . Treat with alcoholic

P3 . Decompose with 

HC1 and dissolve in 

alcohol.

Eg, 1.007.

Pb(C2H3O2) 2 . 1

FT. Evaporate alcohol, add 

dilute HCl, and extract 

with benzene.

R7.

EJ. Fatty-acid 

material, 0.293.

F3 . Evaporate. Extract 

with alcohol.

R5 . Salts. E2 , 3.87.

i Control experiment: 1 gram of palmitic acid dissolved in 300 milliliters of 95-percent alcohol (heated on the steam bath) gave no indication of precipitation with an excess of alcoholic lead acetate solution. What applies to palmitic acid in this respect very likely applies 

to other common fatty acids.

The aqueous filtrate (F3) from the precipitate of 

humic material, produced on acidifying with hydrochloric acid, was evaporated and the residue extracted 

with alcohol a few times until the salts were white. 

The final material soluble in a little alcohol (E2 ) 

weighed 1.80 grams and the total 3.87 grams, as shown 

in table 6. Practically none of it was soluble in benzene. Its further treatment is also described below 

with that of the other portions.

ADDITIONAL, EXTRACTIONS

The whole extraction with dilute alkali was repeated 

twice on the same material with 5 percent potassium 

hydroxide, and a fourth time with 10 percent potassium 

hydroxide. The yields of the separate fractions are 

shown in table 6.

TABLE 6.— Yields of fractions extracted from 868 grams of sediment on successive treatments with caustic alkali solutions

Treatment

1. 2 percent NaOH_ -__ 

2. 5 percent KOH _____

3. 5 percent KOH__-_.

4. 10 percent KOH __ _

Total __ _ _ _

Humic 

acid (P2)

0. 312 

.307

.029

Trace

. 648

"Soluble 

humic 

acid" (Rs)

0. 280 

. 302

. 131

.294

1.007

Fatty-acid 

material 

(Ei)

0. 045 

. 097

.074

.076

.293

Soluble 

organic 

matter (E2)

1. 80 

1. 58

. 38

. 11

. 387

Probably a stronger alkali would have hastened the 

extraction somewhat. The final residue after four 

treatments was light gray when dry and contained 

very little remaining organic matter, as shown by the 

fact that on heating some of it in a test tube there was 

scarcely any detectable ordor of organic matter, and 

no tarry or visible fumes of organic matter appeared.

The same observation was made with the residue 

remaining from the extractions with ammonia. During the course of the extractions the color of the residues lightened appreciably and the yields of organic 

matter successively decreased. From these facts it is 

concluded that practically all the organic matter was 

removed from the sample.

EXAMINATION OF THE FATTY-ACID MATERIAL (Ei)

Fraction EX was examined by the Varrentrap method 

for the presence of unsaturated liquid and saturated 

solid fatty acids. The method is directly applicable 

to mixed free fatty acids.25 The acid material was 

dissolved in about 25 milliliters of 95 percent alcohol 

and titrated to neutrality with tenth-normal sodium 

hydroxide, using phenolphthalein indicator. The alcohol was then largely evaporated, diluted to 50 milliliters with water, and heated, and an aqueous solution 

of lead acetate was added in excess, which precipitated 

practically all the fatty-acid material. After filtering, 

the evaporated filtrate gave a residue consisting of the 

excess of lead acetate reagent with practically no indication of organic matter. The filtered lead precipitate 

was carefully dried at low temperature and extracted 

with ether, which is supposed to dissolve the lead salts 

of the liquid fatty acids. This separation was apparently not complete, as only 0.0127 gram of liquid acids 

was obtained out of a total of 0.2925 gram.

Both portions were therefore again combined and 

then separated into different fractions by fractional 

precipitation of their magnesium salts with alcoholic 

magnesium acetate solution, according to the method

25 Fryer, P. J., and Weston, F. E., Technical handbook of oils, fats, and waxes 

vol. 2, pp. 172-173, Cambridge, 1918.
78 SHORTER CONTRIBUTIONS TO GENERAL GEOLOGY, 1936

of Heintz.26 The alcoholic solution was concentrated 

until an appreciable fraction was precipitated. This 

was filtered off and the solution concentrated further, 

giving a second fraction, and so on until seven fractions 

had been obtained and a final mother liquor remained. 

Each fraction was then recrystallized from hot alcohol, 

the filtrate from each fraction being added to the solution of the next one. A freshly prepared solution of 

magnesium acetate was used. The several magnesium 

salts were eventually decomposed with a few miUiliters 

of 20 percent hydrochloric acid, and the free acids were 

extracted with benzene. The observations made on 

these acids are given in table 7.

TABLE 7.—Observations on organic acids fractionally precipitated as magnesium salts

Number of 

fraction

Percent of 

total fattyacid material

Character Further fractionations

4.7 Solid, light color, melting above 50°

5.6 .do.

7.8 

15.5

15. 1

23.2

A little soft. Amber color becoming 

noticeable. Melted from 43° to 48°.

Similar in appearance to no. 3. Melted 

from 44° to 48°.

Increasing softness and color. Melted

below 39°. 

Somewhat soft at 33°. Darker amber

color than no. 5.

5.8

22.3

Somewhat soft at room temperature. 

Amber-colored.

Amber oil-like at 33°. The oil readily 

flowed together after marking with a 

needle point.

1. The fraction was dissolved in a little alcohol, leaving a small 

proportion of residue. This was dissolved in hot alcohol, 

precipitated with Mg(OAc) 2 , and the precipitate converted into free acid, which melted from 53° to 63°.

2. On adding Mg(OAc) 2 to the filtrate an acid was eventually 

obtained that melted from 68° to 71°.

3. The last filtrate was evaporated to dryness with an excess of 

Mg(OAc) 2 . When taken up in a little alcohol the insoluble part yielded an acid that melted from 62° to 64°. 

The part soluble in alcohol yielded an acid that melted 

over a wide range below 55°.

1. The fraction was dissolved in a little alcohol, in which a 

slight insoluble precipitate that was not filtered remained.

2. A partial and direct precipitation with Mg(OAc)2 yielded a 

light-colored precipitate from which was recovered a little 

soft free acid material that melted from about 53° to 63°.

3. From a further second precipitation with an excess of 

Mg(OAc) 2 was obtained free light-colored solid acid that 

melted from 63° to 67°.

4. Filtrate evaporated to dryness with excess of Mg(OAc) 2 

and taken up with a little alcohol. The insoluble part 

yielded acid material that melted from 45° to 55°. The 

acid material from the soluble fraction was somewhat 

viscous at room temperature.

Nos. 3, 4, 5, and 6 dissolved together in a small volume of 

alcohol.

1. A little insoluble material was filtered. This material was 

viscous at 33° and was light straw-colored. On dissolving 

in a small amount of heated alcohol, a precipitate formed 

with Mg(OAc) 2 .

2. A first partial precipitation with Mg(OAc) 2 yielded light 

straw-colored acid material that melted from 45° to 48°.

3. A second partial precipitation with Mg(OAc) 2 yielded a 

little darker acid material that melted from 40° to 43°.

4. Further fractionation was obtained from filtrate 3 by eyaportion to dryness with an excess of Mg(OAc) 2 and taking up 

with a little alcohol. 

4a. The insoluble fraction yielded straw-colored acid material

that melted below 37°. 

4b. The soluble fraction yielded straw-colored acid material

that was soft at ordinary temperature.

Dissolved in a small volume of alcohol. Direct precipitate 

with Mg(OAc) 2 slight. After evaporation with an excess of 

Mg(OAc) 2 to dryness, some insoluble material was obtained 

on taking up in a little alcohol. This yielded viscous acid 

material that melted below 35°. From the filtrate soft acid 

material was obtained in which needle markings flowed 

together.

Dissolved in a small volume of alcohol. Insoluble material 

slight. A small amount of precipitate formed directly with 

Mg(OAc)2 which yielded soft viscous acid material. The 

filtrate yielded liquid oil.

The range in melting point of the fatty acids was 

thus found to extend from below 37° to 71° and is 

typical of the fatty acids commonly found as esters in 

vegetable and mineral oils. Common saturated fatty 

acids and their melting points are: Stearic, 69.5°; 

palmitic, 63.5°; myristic, 57.5°; lauric, 47.5°; and

28 Holde, D., The examination of hydrocarbon oils and saponifiable fats and 

waxes, tr. by E. Mueller, p. 378, New York, John Wiley & Sons, 1922.

capric, 31.4°. The last two are found in vegetable oils. 

Although the oils in living matter are generally high 

in unsaturated constituents, the sediment examined 

was relatively low in such substances. Thus there 

seems to be no doubt that fatty acids were identified 

as such in the final tests and that they were present in 

the original organic matter in some form insoluble in 

hot alcohol. With the fatty-acid material there may
SOME OKGANIC CONSTITUENTS OF A EECENT SEDIMENT 79

have been some related acids, as indicated by the low 

melting points of the first subtractions of fractions 1 

and 2 (table 7). Their magnesium salts were less 

soluble than those of the succeeding fractions of acids 

having higher melting points. Methods for the 

identification of such possible compounds, however, 

will have to await further research.

The portion E2 was tested for carbohydrates by the 

Molisch reaction 27 with alpha-naphthol, and a distinct 

positive reaction obtained. The nature of the carbohydrate was revealed further by the aniline acetate 

test, which showed that some pentose and possibly a 

little hexose, such as fructose or sorbinose, was present.

A portion of E2 weighing 0.4168 gram was dissolved in 

about 25 milliliters of water, 0.25 gram of sodium 

hydroxide added, and the solution evaporated to

M Mulliken, S. P., The identification of organic substances, vol. 1, p. 26, New 

York, John Wiley & Sons, 1904.

dryness. The material was extracted several times 

with warm alcohol, which dissolved the remaining 

sodium hydroxide but very little organic matter. The 

brown residue, easily powdered, gave 6.3 percent of 

ash on ignition. Apparently a sodium salt of the 

material was formed which was insoluble in alcohol, 

although the material before conversion to the sodium 

salt was soluble.

Sodium hydroxide has long been used in extracting 

the organic matter of soils, and a considerable number 

of compounds have been thus isolated and identified. 28 

For some constituents, portions weighing 50 pounds 

were necessary in order to obtain identifiable quantities 

of the organic compounds. Similar methods might 

well be applied to sediments.

28 Shorey, E. C., Some organic soil constituents: U. S. Dept. Agr., Bur. Soils, 

Bull. 88,1918.

o