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doi: 10.1130/0016-7606(1954)65[1183:SDOLSI]2.0.CO;2 1954;65, no. 12;1183-1198Geological Society of America Bulletin

F. M SWAIN and N PROKOPOVICH IN CEDAR CREEK BOG, MINNESOTASTRATIGRAPHIC DISTRIBUTION OF LIPOID SUBSTANCES

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BULLETIN OF THE GEOLOGICAL SOCIETY OF AMERICAVOL. 65. PP. 1183-1198. 5 FIGS. DECEMBER 1964

STRATIGRAPHIC DISTRIBUTION OF LIPOID SUBSTANCES INCEDAR CREEK BOG, MINNESOTA

BY F. M. SWAIN AND N. PROKOPOVICH

ABSTRACT

The lake and bog deposits of Cedar Creek Forest, Isanti and Anoka counties, Min-nesota, consist of a multiple-facies accumulation of marl, peat, copropel, and sapropel.Chromatographic analyses of the lipoid extracts of samples of the sediments show meas-urable amounts of saturated and aromatic hydrocarbons as well as large proportions ofasphalts and polar lipoid compounds. In general composition the "oily" fractions some-what resemble a Venezuelan asphalt. The ratio of total lipoids in the peat, marl, andunderlying sand, respectively, in this deposit is approximately 12:3:1. The highestmeasured content of saturated hydrocarbons occurs just above the marl. The otherfractions show no noteworthy relationship to depth or type of material. Most of thevariation in distribution of the lipoids appears primary, but some shifting of the hydro-carbons may have resulted from movements of ground water within the bog. The datasuggest that the hydrocarbon formation or liberation from the source material tookplace concomitantly with the accumulation of the lake and bog deposits.

CONTENTS

TEXTPage

Introduction 1184Acknowledgments 1185Procedures 1185Results 1189

Paraffin-naphthene fraction 1189Aromatic fraction 1189Asphaltene fraction 1190Inorganic constituents 1190

Discussion 1190General statement 1190Total extractable fraction 1190Saturated hydrocarbons 1191Aromatic hydrocarbons 1193Asphaltic fraction 1194Relationship of present samples to crude oils

and hydrocarbons of other places 1194Post-depositional movements of hydrocarbons 1194Chemical and biochemical stability of the bog 1194Succession in the bog 1195Quantity of extractable material 1196Conclusion 1197References cited 1197

ILLUSTRATIONSFigure Page1. Sketch map of part of Cedar Creek Forest

from aerial photograph 11842. Northwest-southeast cross section through

part of Cedar Creek Forest 11853. Comparison of sedimentary types to total

lipoids, hydrocarbon fractions, and otherproperties at station 1, Cedar Creek Bog... 1192

4. Comparison of chemical composition ofvarious crude oils and of hydrocarbons fromthe Gulf of Mexico with that of hydrocar-bons and asphalts from Cedar Creek Bog. . 1193

5. Hypothetical curve of rate of depositionbeneath station 1, Cedar Creek Bog 1196

TABLESTable Page1. Measurements of pH, Eh, carbon, nitrogen,

and carbon/nitrogen ratios in samples fromCedar Creek Bog 1186

2. Descriptions of samples of which hydrocar-bon analyses were made 1187

3. Chromatographic analyses of lipoid extracts 11894. Partial inorganic analyses of some of the

Cedar Creek Bog samples 11905. Approximate tonnages per acre foot of vari-

ous extractable materials in Cedar CreekBog 1196

1183



1184 SWAIN AND PROKOPOVICH—LIPOID SUBSTANCES

INTRODUCTION

A study of the stratigraphy of bituminousdeposits has led to an examination of the lip-oid1 content of some post-glacial lake and bog

below the present level of the shallow lake.The succeeding deposits up to 11-12 feet belowthe lake consist of marl containing organicmatter of coprogenic nature (copropel)3 with athin traceable layer of dark-brown copropel in

100 200 300 4QQ 500 meters500 1000 1500 feet

FIGURE 1.—SKETCH MAP OF PART OF CEDAR CREEK FOREST FROM AERIAL PHOTOGRAPHShowing locations of stations sampled. A-B, line of stratigraphic section given in Figure 2.

Location of the area is given in the small inset.

deposits in Minnesota. An investigation of thebog and lake sediments of Cedar Creek Forest,Anoka and Isanti counties, Minnesota, wasundertaken because of the limnological andecological studies in this area by several scien-tists, including the outstanding efforts ofLindeman (1941a; 1941b; 1942a; 1942b).

The distribution of lipoids at several locali-ties in Cedar Creek Bog is discussed in thispaper. A further description of the sedimentsof this and other lake and bog materials is inpreparation.

The Cedar Creek Forest area (Fig. 1) is alate-senescent stage bog that originated as alate Wisconsin lake which may be an ice-blockdepression on the Anoka sand plain (Linde-man, 1941a, p. 101). The early deposits of thebasin (Fig. 2) consist of sideritic marl, perhapsearly-eutrophic,2 at a depth of about 35 feet

the middle. Overlying the marl is a layer ofeutrophic finely divided brown copropel andblack sapropel 6-8 feet thick near the lake butthinner toward the bog margins. This is inturn overlain by sedge-peat and then by coarserforest peat and Sphagnum peat up to the pres-ent bog surface. A portion of the bog near thelake is quaking (Fig. 2). The water table fluc-tuates seasonally several feet (Buell, 1941, p.317).

Flint and Deevey (1951, p. 272) using dataassembled by Lindeman show that the bog ispost-Mankato and represents the later part ofpollen zone A (spruce-fir) and all subsequentzones up to the present. The dark-brown cop-ropel layer referred to above occurs in thecopropel-marl subfacies at depths ranging from20 to 30 feet or more (Fig. 2). The layer repre-sents pollen zone B (pine) and has a radiocar-

1 "Lipoid" materials include all the substancesextractable with various petroleum solvents, in con-trast to "lipid" material which refers to saponi-fiable oxygenated fats, exclusive of hydrocarbonand certain other nonsaponifiable ether-solublecompounds.

2 eutrophic, nutritious, referring to lakes contain-ing abundant nutritive salts, as contrasted to oligo-trophic lakes which are poor in nutrients.

3 copropel (kopros, dung + pelos, mud) dark-brown or gray coprogenic ooze, containing chitinousexoskeletons of benthonic arthropods in addition toreworked organic matter. The term is here suggestedto replace gyttja which has had somewhat vagueapplication. Sapropel is black, fine to coarse-tex-tured detritus formed by anaerobic bacterial de-composition of organic detritus in lakes and seas.



INTRODUCTION 1185

bon age of 7988 ± 420 years (Flint and Deevey,1951, p. 272).

ACKNOWLEDGMENTS

Appreciation for their assistance and en-couragement is expressed to Professors G. A.Thiel, J. W. Gruner, H. E. Wright of the De-partment of Geology; D. B. Lawrence, Depart-ment of Botany; S. F. Eddy, Department ofZoology; E. B. Sandell and C. F. Koelsch,School of Chemistry; and H. H. Wade, ActingDirector, Mines Experiment Station, Univer-sity of Minnesota. Mr. P. V. Smith, Jr., Stand-ard Oil Development Company, kindly pro-vided information about the chromatographicmethod of analysis. Paul L. Engel and K. E.Dickinson aided in field and laboratory work.

The study has been supported by grant-in-aid 391-3201-6100 of the Graduate School,University of Minnesota.

Permission to study the Cedar Creek Bogsamples has been granted by the Committee incharge of Cedar Creek Forest, A. N. Wilcox,Chairman.

PROCEDURES

Samples of the bog sediments were obtainedin August 1953 and in January 1954 with aDavis peat-borer and were stored in 300 mltest tubes.

Electrometric determinations of pH and Eh(Table 1) with a Beckman meter were made onthe summer collections about 3 hours aftercollecting; the winter collections froze and de-terminations were made after bringing them toroom temperature 2 days later. Part of eachsample was set aside for further study of theorganic debris and inorganic sediments. Por-tions of 6 samples were taken for C and N con-tent (Table 1).

Fourteen core samples from station 1, rang-ing in depth from 1 to 15 feet, two deep sam-ples from station 2 and a sample from the lakebottom at station 4 were selected for hydrocar-bon analysis. A known portion of each samplewas extracted twice with a mixture of benzene(75%), acetone (15%), and methanol (15%) assuggested by Smith (1952, p. 437). Blank runson the solvent left a residue of less than .01per cent by weight; this was considered satis-factory.




Each wet sample of sediment was Sohxlet-extracted at refluxing temperatures for 8 hours.These extracts were separated from the con-tained sample water in a separatory funnel

of water-pumped nitrogen in a desiccator con-nected to a filter pump. The resulting residues,representing the lipoid content, ranged from0.5 per cent of the total sample in the sand to

TABLE 1. -MEASUREMENTS or pH, EH, CARBON, NITROGEN, AND CARBON/NITROGEN RATIOS IN SAMPLESFROM CEDAR CREEK Boo

Station

11

12344444444

Depth (ft)

3-44-56-77-89-10

11-1212-1313-1414-1535-36

26.5-27.514-1515-1616-1717-1819-2020-2121-2222-23

Lake water

pH_

7.1—

7.3—

7.47.77.25——

7.157.57.57.17.17.57.87.457.47.67.5

Eh (mv)'

+325—

+405—

+365+415+415—

+445+125+ 167+281+ 185+215+224+275'+256+257+299+475

%ct

-t47.23

—47.5948.01

9.78—

15.13—8.47——————————

%Nt

—2.31

—2.773.360.9

—0.75

—0.9——————————

C/N

—20.4—

17.214.310.8—

20.2_

9.4—————

—— .———

* Corrected for potential of calomel reference electrode, the E0 of which is taken as +245 mv at roomtemperature

t School of Chemistry, University of Minnesota, J. L. Swenson and O. Runquist, microanalystst Not determined

involving several stages of separation anddilution with fresh solvent. The samples werethen dried at 105°C and extracted with freshsolvent for a second 8-hour period. The distillatewas clear long before the end of the extractionperiod. Some additional lipoids may have be-come available as a result of the drying; Waks-man (1936, p. 159) quoting Schneider andSchellenberg states that the ether-soluble frac-tions of peat and coal increase with a rise intemperature during extraction under pressure.Neither the wet nor dry sample extracts showedfluorescence. Hydrocarbon analyses were runseparately on the wet and dry extracts of twosamples; no appreciable differences in resultswere found, so the extracts were combined.

After reduction by distillation, evaporationof the solvent was accomplished with a stream

9.7 per cent in the middle part of the peat(Table 2).

Each lipoid residue was then separated bychromatography involving elution of successivefractions from a column of activated alumina(Harshaw, A1-0109-P) using the procedure de-scribed by Smith (1952, p. 437-39). Normalheptane, benzene, pyridine, and acetone werethe successive eluting agents.

The following ratio of alumina and solventswas used:

8 g alumina5 ml N-heptane prewet

12 ml each of N-heptane and benzene9 ml pyridine6 ml acetone

The amount of the heptane cut, dried to con-stant weight under nitrogen, was taken as the



PROCEDURES 1187

TABLE 2.—DESCRIPTIONS OP SAMPLES

Station

1

1

1

1

1

1

1

1

11

1

1

Depth(ft.)

1-2

2-3

3-4

4-5

5-6

6-7

7-8

8-9

9-1010-11

11-12

12-13

Description of dried sample

Med. gray-brown, med. and coarse-tex-tured peat; a few carbonized frag-ments; cell structure well preserved

Med.-dark gray-brown sapropel-copro-pel-peat and peat-copropel, finely tex-tured; Daphnia exoskeletons; insectparts; more hygroscopic than 1-2 ft.

Med.-dark gray-brown, slightly sandycopropel-peat; coarser than 2-3 ft.;fine fraction dark brown, resinous,with coprogenic pellets; few ostracodesand exoskeletons of other benthos

Med. gray-brown, very fibrous copropel-peat, finer-textured than 3-4 ft. ; manyinsect parts, Cyclops, Daphnia; abun-dant pollen; slightly sandy

Med. gray-brown, coarsely fibrous co-propel-peat; matrix of dark-brown,resinous, coprogenic pellets and ir-regular aggregates; few Daphnia andother chitinous exoskeletons

Dark gray-brown, finely fibrous sapro-pel-copropel-peat, some chitinous exo-skeletons, few ostracodes

Dark gray-brown, finely fibrous, tenace-ous sapropel-peat-copropel; veryfinely divided copropel forms most ofmatrix; peaty portion mostly pond-weeds; few seeds; very few arthropodexoskeletons

Dark gray-brown peat-copropel-sapro-pel; finely divided black and brownresinous organic matter and finelydivided peat; insect parts; carbonizedfragments; sand grains

Same as 8-9 ft.Dark gray-brown to black copropel-

peat-sapropel, with most of thecoarser particles partly decayed darkbrown, resinous; pondweed fibers;Daphnia and other exoskeletons;seeds; pollen; scattered fine-coarsequartz grains

Very light-gray, microgranular, soft,porous, partly sandy marl; white,altered mollusk fragments; seed pods,Daphnia exoskeletons

Very light-gray, soft, porous, very sandymarl; seed pods

Dry wt. ofsample

(gm)

2.0030

1.9495

1.3610

0.9830

1.5008

1 . 1933

1.4550

1.6610

2.21701.9080

4.4100

7.3530

Moisture%

88

89

91

94

90

93

93

87

8990

68

56

Wt. oflipoids(gm)

.1460

.1073

.0694

.0783

.0921

.0741

.0874

.1612

.1586

.0819

.0679

.0951

Lipoids%of

sample

7.3

5.5

5.1

7.9

6.1

6.2

6.0

9.7

7.14.3

1.5

1.3




TABLE 2.—Continued

Station

1

1

2

2

2

Depth(ft.)

13-14

14-15

12-13

25-26

35-36

Description of dried sample

Light-gray to pale buff, sandy, copropel-marl; soft, porous; sand, finely granu-lar marl, and copropel intimatelyintermixed; exoskeletons of Daphnia,etc.; seed pods

Light-gray, subangular to well-roundedfine- to medium-grained, slightly car-bonaceous and bituminous sand; fewrock fragments

Light gray-brown, microcrystalline,platy, and granular- textured ostra-codal copropel-algal marl; copropel ismedium to light brown and is mixedwith finely granular marl; platy marlfragments evidently represent depo-sition around leaf stalks of Potamoge-ton or other pondweed; they show im-pression of cell structure on one sideand a porous fabric on the other; ostra-codes include Candona cf. caudata,Darwintda stevensoni, Cypridopsisvidua, and Cypria lacustris

Light dove-gray, soft, porous, micro-granular copropel-marl, with abun-dant poorly preserved fragile ostra-codes and Daphnia; many rust-brownspots probably due to oxidation ofsiderite when sample was dried (Seeanalysis, Table 4.)

Light rust-brown, microgranular, verysideritic marl (see Table 4); freshsamples dark gray to black; few ostra-codes, including Candona sp., Cyclo-

Dry wt. ofsample

(gm)

4.9610

7.5910

3.6704

5.6403

5.2058

cypris sp.

Moisture%

70

61

79

—

71

Wt. oflipoids(gm)

.1065

.0355

—

.0722

.0847

Lipoids%.of

sample

2.1

0.47

—

1.2

1.6

paraffin-napthene fraction, the benzene cut asthe aromatic fraction, and the pyridine-plus-acetone cut as the asphaltene fraction. Thebenzene and especially the pyridine cuts weredifficult to bring to constant weight. The re-sults are given in Table 3. The combinedhydrocarbons averaged 0.68 per cent of thetotal sample (dry weight) in the peat, 0.17 percent in the marl, and was 0.14 per cent in thebasal sandy subground of the bog. The termsparaffin, naphthene, and aromatic are used forconvenience; pure compounds of members ofthese series have not been determined by chemi-cal analysis because of the small size of the

samples obtained. It is hoped that eventuallyenough peat can be extracted to provide aresidue suitable for regular chemical analysis.Smith (1954, p. 384), working with larger sam-ples, demonstrated the presence of severalhydrocarbon series in chromatographic separa-tions of extracts from Recent marine sediments.

The reproducibility of the analyses variedfrom 0.2-11 per cent in the nine fractions, ofwhich duplicates were studied. The 3 principalsources of error are: (1) the volatility of thelipoid extracts make it difficult to maintainconstant weight, (2) it is difficult to dissolveeach fraction completely and transfer it to the



PROCEDURES 1189

column without slight losses, and (3) some ofthe fractions may be unstable at room tem-perature. Smith (1954, p. 387) found no evi-dence of changes in the hydrocarbon corn-

cent of the lipoid extract. In all samples theresidue consisted of colorless, slightly odorouslight oil, exhibiting pale-blue fluorescence. Sev-eral samples contained colorless bladed or hair-

TABLE 3.—CHROMATOGRAPHIC ANALYSES OF LIPOID EXTRACTS

Depth PredominantMaterial

Paraff-Naphth

%HC %Lip

Aromatic

%HC %Lip

Asphaltic

% LipoidsRemaining on

Alumina % Lip.Combined HC% of Sample

Sta. 1

1-22-33-44-55-66-77-88-99-10

10-1111-1212-1313-1414-15

peatcopropelpeatpeatpeatpeatcopropelsapropelsapropelsapropelmarlsandy marlmarlsand

44.527.534.047.092.060.040.50

40.093.040.524.566.029.0

5.91.15.67.72.58.43.2—0.9

29.84.23.45.18.3

55.572.566.053.08.0

40.059.5

100.060.07.0

59.574.534.071.0

7.53.0

10.98.50.25.54.74.81.32.26.1

10.22.6

19.7

28.428.435.230.824.327.026.711.714.528.034.523.429.344.3

58.267.548.353.073.059.165.483.583.340.055.263.063.027.7

0.980.220.851.270.170.870.480.480.161.380.160.180.170.14

Sta. 2

25-2635-36

marlsideritic marl

65.030.0

8.65.5

35.070.0

4.610.9

26.021.9

60.86.17

0.170.29

Sta. 4

12-13 copropel 32.4 2.5 67.5 5.2 30.8 61.4 0.12

pounds, such as formation of aromatics fromolefine compounds during the chromatographicseparation. Despite the small residues left afterblank runs with solvents, a possible source oferror lies in the formation of lipoids from theacetone.

Two of the heavy pyridine cuts were elutedfrom fresh columns with pyridine and acetone.No residue remained on the alumina, indicat-ing that the previous separation had been com-plete.

RESULTS

ParaJJm-Naphthene Fraction

This fraction formed up to 93 per cent byweight and averaged 46 per cent of the hydro-carbon portion of the samples, and up to 30 per

like crystals, showing high-order birefringenceand parallel extinction.

Aromatic Fraction

This cut formed up to 100 per cent averag-ing 54 per cent of the hydrocarbon portion ofthe sample and up to 20 per cent of the lipoidfraction. Most of the aromatic residues wereodorous pale-yellow heavy oil or wax withtiny disseminated colorless granular or needle-like crystals. The aromatic fraction at 3-4feet (station 1) had long hairlike crystals likethose hi some of the paraffin fractions and wasthe darkest. The 5-6 foot fraction was colorlessoil. Most of the aromatic fractions showed paleyellow-green to gold weak to bright fluores-cence, but the 2-3 foot and the 6-7 foot residueshad blue fluorescence. The 14-15 foot residue




was especially difficult to bring to constantweight and continued to give off a strong odorshowing presence of volatile components andpointing to the unreliability of the tabulatedpercentages at this level. In the 35-36 foot

TABLE 4.—PARTIAL INORGANIC ANALYSES OF SOMEOF THE CEDAR CREEK BOG SAMPLES*

Sta-tion

111112

Depth(feet)

4-57-89-10

11-1213-1435-36

CaCOj

7.996.887.11

74.8040.7538.60

MgCOi

0.960.900.882.372.051.13

S04

nilnilnilnilnilnil

TotalSt

0.210.320.800.371.460.43

TotalFet

2.271.591.721.042.01

15.63

TotaP§

——

0.0210.0360.255

* Analyses by Mines Experiment Station, Uni-versity of Minnesota, Vernon Bye, Analyst

t May be present as sulfide, native sulfur, or asan organic compound

J May occur as siderite, ankerite, marcasite, fer-rous sulfide hydrate, or in some other form

§ May occur as inorganic apatite, vivianite(Fe3P2O8-8H2O), bobierrite (MgsPzOj-SHsO), or asorganic phosphate ("cellophane").

sample during elution, a narrow red bandformed at the heptane-benzene front andmoved down with the benzene, which then be-came yellow-orange. In the other elutions theheptane-benzene front was followed by bluefluorescence of the benzene. The fluorescence ofthe benzene is caused by some impurity (Prof.R. Livingston, Dept, of Chemistry, Univ. ofMinnesota), but this was not detected in theblank runs on the solvent.

Asphaltene Fraction

The pyridine and acetone cuts constitute theasphaltic portion of the extracts plus an un-determined amount of nonpolar organic com-pounds containing oxygen, nitrogen, andpossibly sulfur. This fraction far exceeded theother two in most of the samples, averaging 27per cent and attaining 44 per cent of the totallipoids in the 14-15 foot sample at station 1.The asphalts consisted of light to dark yellow-brown and greenish-brown heavy oil and waxwith a tarry odor. The fractions at 2-3 feet, 6-7feet, 10-11 feet, station 1, and 35-36 feet, sta-

tion 2, were very viscous and sticky. The 6-7and 7-8 foot fractions were reddish brown. Theasphaltene fractions fluoresced not at all orrarely weak golden to orange. The fractionswere characteristically clear; a few asphaltfractions contained particulate material.

Inorganic Constituents

Partial chemical analyses were made of asmall residual part of several samples (Table 4)to determine any possible relationship betweenthe inorganic constituents and the occurrenceof the hydrocarbons.

DISCUSSION

General Statement

The stratigrapher should find value in theinformation obtainable from similar chromato-graphic analyses of extracts from bituminoussedimentary rocks. For example, Nevin (1945,p. 285) pointed out that in Upper Devonian(Genesee) black shale of New York State a facieschange from carbonaceous on the east to bitumi-nous on the west could be recognized by theamount of oil obtainable by distillation from theshales. Because of the small amount of equip-ment and the relative ease and rapidity of mak-ing the analyses, chromatographic analysis ismuch more adaptable to stratigraphic studiesthan are processes of fractional distillation thathave been applied to study of crude oils (New-mann et al, 1941; Barr, et al, 1943; Tulsa Geol.Soc. Res. Comm., 1947).

In the present study, many bottom samplesfrom lakes in Minnesota, and bituminous rocksamples of several ages are being analyzed tolearn more about the possible stratigraphicvalue of the lipoid substances.

Total Extraciable Fraction

The materials extractable from peat withpetroleum solvents and alcohol, include, inaddition to hydrocarbons and "asphaltene",resins, nitrogenous fats, tannin, bitter sub-stances, alkaloids, chlorophyll, and some carbo-hydrates (Waksman, 1936, p. 278). In chroma-tographic separation a large part of thesesubstances other than hydrocarbons and as-



DISCUSSION 1191

phaltene remain adsorbed on the alumina andcolor it green or brown.

In the deposit studied, the only clear-cutrelationship between the kind of bog materialand the total extractable fraction is that theextractable fraction decreases from the base ofthe peat downward into the marl. The rela-tively high lipoid fraction in the 8-9 and 9-10foot samples (Table 2) is partly the result ofthe increase of nitrogenous compounds (Table1) because of microbial decomposition of car-bohydrates during the formation of the peat(Waksman 1936, p. 277). The high lipoid con-tent just above the marl is probably due alsoin part to the relatively higher fat content ofthe original plankton-rich source material. Con-siderable microbial activity occurs on the mar-gin of bog lakes, where sedge growth is dense.This causes patches of sapropel to form in theshallow near-shore waters as well as in thehypolimnion zone of off-shore parts of the lake.In the Cedar Creek basin, such material shouldform along the peat-marl front as the peatyportion advanced upon the marl toward themiddle of the bog (Fig. 2).

Waksman states (1936, p. 278) that "low-moor" peats, such as those studied here, con-tain less ether- and alcohol-extractable sub-stances than "highmoor" (Sphagnum-rich)peats, which are reported to have 20 per centor more "bitumen". Pollen-rich peats containthe most extractables. An increase in age inSphagnum peat is marked by an increase in ex-tractables; in lowmoor peats this is not alwaysso, both because of an original deficiency ofcellulose in the form of woody tissue and be-cause of a lower decomposition rate in themore stable, lignin-rich lowmoor peats. In thepresent samples little or no Sphagnum peat wasfound. These plants are present mainly in theupper few inches of the bog. In the 4-5 footsample the slight increase in lipoids may berelated to the abundant pollen noted at thathorizon.

Saturated Hydrocarbons

The hydrocarbon portions of "peat wax"have not been studied in detail, although solidparaffins, such as triacontane (CsoHea) andpentatricontane (CssH^), forming 15-20 per

cent of the wax have been reported (Titow,1932, p. 266). A solid hydrocarbon, hen triacon-tane (C3iH64), was extracted from peat withboiling alcohol (Schreiner and Shorey, 1911, p.83).

In the present samples, the quantity ofsaturated hydrocarbons of the paraffin andnaphthene series varies. It has not yet beendetermined whether this variability is traceablyconsistent within the bog, and whether it is re-lated to original variation in source material,state of decomposition, or other factors. Thereis no direct increase of the hydrocarbon frac-tions with increased depth such as has beenreported for total lipoids in a Maine peat bog(Waksman, 1936, p. 269). The high content ofsaturated hydrocarbons at 10-11 feet, amount-ing to more than 1 per cent of the total sample,probably represents an original accumulationrather than a concentration of the hydrocar-bons from higher levels.

The sources of the saturated hydrocarbonresidues are probably fats or lipids of the plantand animal cytoplasm, and decomposed cellu-lose. Bacterial decomposition of cellulose, ifcarried to final stages, produces varyingamounts of methane gas in two principal steps(Ruttner, 1953, p. 171):(1) hydration of cellulose and formation of

hexose (glucose):

C6H1006 + H2O = C6H12O6;

(2) a series of reactions ending with methaneformation under anaerobic conditions, butin an alkaline environment:

C6H12O6 = 3CO2 + 3CH4.

Methane is formed by specialized bacteria ofwhich Methanosarcina is one of the most im-portant (Liebmann, 1950, p. 14). These bac-teria occur in an entirely anaerobic layer incopropel where, unable to utilize fresh cellulose,they form methane from decomposed productsof low molecular weight, as fatty acids, alco-hols, and ketones. The concentration ofsaturated hydrocarbons at 10-11 feet (Table 3)may have resulted partly from such a reductionof carbohydrates along the advancing peat-marl front.

Other gaseous hydrocarbons, includingethane, propane, ethylene and propylene, have




recently been detected in glucose fermentation The crystals observed in some of the satu-(Davis and Squires, 1954, p. 381). rated fractions were not identified specifically,

It is uncertain whether cellulose itself was an but their habit is like that in normal paraffinimportant source. Waksman (1936, p. 279) from C24H5o to C44H90 (Sachanen, 1945, p.cites data to show that in lowmoor peats cellu- 307). Kolvoort (1938, p. 338) observed a change

column l%oflipoids| hc + as0 2 4 6 8 10 rem.lip

.fie. I PH I Eh I C/Nasph. 7 75 8 (Volts) o ip 20

O .1 .2 .3 4

COPROPELI-Insect parts

FIGURE 3.—COMPARISON OF SEDIMENTARY TYPES TO TOTAL LIPOIDS, HYDROCARBON FRACTIONS, ANDOTHER PROPERTIES AT STATION 1, CEDAR CREEK Boo

lose and hemicellulose are both relatively lessimportant than the more resistant lignin.

Measurable amounts of saturated hydrocar-bons occur at shallow depths in the bog, show-ing that their liberation from cytoplasm or for-mation by decomposition of carbohydrates isaccomplished simultaneously with the accumu-lation of the bog debris. This rate of accumula-tion based on the C14 date of 8000 years at adepth of about 25 feet would be approximately320 years per foot; this average is subject tomany modifications owing to change of climate,variations in plant populations, etc.

in crystal system within normal C24H60 withincreasing temperature up to the melting pointat approximately 50°C: below 41 °C crystals ofthis hydrocarbon are twinned plates and proba-bly monoclinic (7-form); at 41° the system istransitional to a twinned orthorhombic form(/3-form), and at 46° it is transitional to proba-bly hexagonal needles (a-form); at the transi-tion points, the two types may exist in equilib-rium. Both needles and plates were observedin the residues, but no further study of them wasmade. Sachanen (1945) reports an extensiveliterature on the petroleum wax crystals.



DISCUSSION 1193

Aromatic Hydrocarbons

The data show that aromatic hydrocarbonsare present in significant amounts close to thebog surface. Lignins contain aromatic nuclei

PARAFFIN - NA PHTHENE

formula CnH2n_4 and are like the aromatics inhaving only carbon atoms in the ring structure(homocyclic) but are more saturated, is the sapof coniferous trees; pinene, CioHi6, the principalconstituent of turpentine, is the commonest

A. Composition of crude oils (circles) (data fromSachanen, 1945) and recent samples from Gulf ofMexico sediments (discs) (data from Smith, 1952).

(1) Paraffin crude oil (paraffins 40%, naphthenes48%, aromatics 10%, resins and asphalts 2%).

(2) Naphthene crude oil; Emba-Dossor crude(paraffins 12%, naphthenes 75%, aromatics 10%,resins and asphalts 3%).

(3) Naphthene crude oil; Baker crude (paraffins9%, naphthenes 66%, aromatics 19%, resins andasphaltics 6%).

(4) Natural asphalt; Bermudez (paraffins 5%,naphthenes 15%, aromatics 20%, resins and as-phalts 60%).

(5) Paraffin-naphthene crude oil; Oklahoma Citycrude (paraffins 36%, naphthenes 45%, aromatics14%, resins and asphaltenes 5%).

(6) Naphthenic-aromatic crude oil; Santa FeSprings, California crude (paraffins 20%, naphthenes45%, aromatics 23%, resins and asphaltenes 12%).

(7) Naphthenic-aromatic crude oil; Borneo crude(paraffins 15%, naphthenes 35%, aromatics 35%,resins and asphaltenes 15%).

(8) Mixed asphaltic crude oil; Inglewood, Cali-fornia crude (paraffins 8%, naphthenes 42%,aromatics 27%, resins and asphaltenes 23%).

(9) Mixed asphaltic crude oil; Perm, Russiacrude (paraffins 13%, naphthenes 15%, aromatics40%, resins and asphaltenes 32%).

(10) Recent, Gulf of Mexico 3-4 feet (paraffin-naphthene 28%, aromatics 7%, asphaltic 65%).

(11) Do, 18-22 feet (paraffin-naphthene 55%,aromatics 7.7%, asphaltic 37.3%).

(12) Do, 102-103 feet (paraffin-naphthene 60.7%,aromiftics 13.8%, asphaltic 25.7%).

(13) Recent, Laguna Madre, Texas (reducingenvironment) (paraffin-naphthene 60%, aromatic6.6%, asphaltic 33.4%).

(14) Do (oxidizing environment) (paraffin-naphthene 4%, aromatic 1%, asphaltic 95%).

B. Composition of nonpolar lipoids; samplesfrom Stations 1 and 2, Cedar Creek Bog. (Depthsin feet)—15, 1-2; 16, 2-3; 17, 3-4; 18, 4-5; 19, 5-6;20, 6-7; 21, 7-8; 22, 8-9; 23, 9-10; 24, 10-11; 25,11-12; 26, 12-13; 27, 13-14; 28, 14-15; 29, 25-26-30, 35-36.

FIGURE 4.—COMPARISON op CHEMICAL COMPOSITION or VARIOUS CRUDE OILS AND HYDROCARBONSFROM THE GULF OF MEXICO WITH THAT OF THE HYDROCARBONS AND ASPHALTS

FROM CEDAR CREEK BOG.

AROMATIC ASPHALTIC

PARAFFIN-NAPHTHENE

ASPHALTIC

(Erdtman, 1943, p. 11), and this portion of theorganic matter along with that derived fromthe lipoids may have contributed to the aro-matic fraction of these samples. There is somequestion, however, whether lignin can be de-composed under water (Ruttner, 1953, p. 172)since it is attacked predominantly by aerobicfungi which do not commonly occur in water.A source of terpenes, which have the general

natural terpene (Conant and Blatt, 1947, p.531). Waksman (1936, p. 231) reports up to25 per cent of benzol- and alcohol-soluble ma-terial in old pine needles, which may be relatedto aromatics and terpenes in composition.

Most of the benzene residues were heavilyloaded with tiny needle-like or platy crystals.In general the aromatic crystals are muchsmaller than the paraffmic crystals and show




lower-order birefringence; the needle crystalshave parallel extinction. Such aromatic com-pounds as naphthalene and anthracene arecrystalline at room temperatures and may bepresent in the crystalline substance found inthe aromatic cuts.

Asphaltic Fraction

This forms up to 44 per cent of the lipoidsand up to 2 per cent or more of the entire sam-ple; the high value occurring in the 1-2 footdepth. The asphaltic residues varied more thandid either of the hydrocarbon cuts. This varia-tion between samples in color, viscosity, andodor is probably more important from the pointof view of the origin and stratigraphy of thedeposit than the actual quantity of asphalticsin individual samples. For instance, the sampleswhich contained many Daphnia and otherchitinous arthropod exoskeletons produced verysticky asphalt residues.

The asphaltic fraction differs strikingly fromthe saturated and aromatic hydrocarbons inthat it is darker brown and green, weakly ornot at all fluorescent, and lacks disseminatedcrystals. There may be an inverse relationshipbetween the coarseness of texture of the peatand the ratio of hydrocarbons plus asphalts tothe remaining lipoids (Fig. 3); the sapropelicand copropelic fractions tend to have the largerproportions of polar substances remaining onthe alumina.

Relationship of Present Samples to Crude Oilsand Hydrocarbons of Other Places

The chemical composition of several types ofcrude oils has been given by Sachanen (1945,p. 421-426). Sachanen's analyses are plottedin Figure 4A after combining his paraffin andnaphthene percentages to provide a comparisonwith the present analyses. Chromatographicanalyses of hydrocarbons from the Quaternaryof the Gulf of Mexico, determined by Smith(1952, p. 438) are also plotted in Figure 4A. TheCedar Creek Bog analyses are plotted inFigure 4B. Except for the sample at the base ofthe peat (No. 24), the Cedar Creek samplesare all highly asphaltic, resembling such de-posits as the asphalt from Bermudez Lake,Venezuela. The aromatic content of the Cedar

Creek samples, however, is similar to that ofseveral high-grade crude oils. The samplesstudied by Smith from cores and bottom sam-ples taken in the Gulf of Mexico average moresaturated hydrocarbons than those from CedarCreek Bog.

POST-DEPOSITIONAL MOVEMENTS OFHYDROCARBONS

The lighter liquid and gaseous hydrocarbonsthat may have been present in the sampleswere not detected. That such materials mighthave been in the samples is suggested by theexperiments of Davis and Squires (1954) whowere able to obtain ethane, propane, ethyleneand propylene in glucose fermentation. Ineutrophic lake and bog deposits large quantitiesof methane are produced, a large proportion ofwhich escapes into the air. It has been observedin sampling various lake bottoms that largebubbles of methane come to the surface whenthe sediment is disturbed; on the other hand,no methane was detected in the test holes inCedar Creek Bog. The gas is evidently pushedout of the sediments during compaction (Jamineffect).

The variable distribution of the lipoid com-pounds in the samples studied is mainly pri-mary, resulting both from original differencesin the source material and in the rate andamount of decomposition. Subsequent move-ment of the oils and waxes probably resultsfrom water movements, but some migrationmay be effected by expulsion of the gases. Thewater movement may be principally of twokinds: upward expulsion of the mobile lipoidsas emulsion with the water during compaction;and lateral movements along separation planeswithin the flexible mass of peat and marl. Theentire bog surface fluctuates to correspond withseasonal precipitation (Buell, 1941, p. 317), andthe accompanying movement of water in thebog is probably more lateral than vertical.

CHEMICAL AND BIOCHEMICAL STABILITYor THE BOG

In the pond in Cedar Creek Bog Lindeman(1941b) found the following range in condi-tions: oxygen 0-150 per cent of saturation, pH6.8-9.4, total alkalinity 38-107 mg/1., calcium



CHEMICAL AND BIOCHEMICAL STABILITY OF BOG 1195

31-92 mg/1., magnesium 7-17 mg/L, iron0.2-20 mg/1. He found this a highly productivepond; the ratio of producers to consumers is70.3:8.3, as expressed in calories per squarecentimeter.4

The firm portions of the bog away from thesmall pond are at present fairly stable judgingfrom the mildly oxidizing Eh values obtained(Table 1). Beneath the pond, there is bacterialactivity at the anaerobic level as evidenced bythe somewhat reducing Eh values found therein midwinter 1954. Lindeman (1942a, p. 1)found that anaerobiosis prevailed in the bot-tom waters of the pond for 51 days in mid-winter 1940. The reducing capacity of thesediments collected at station 4 just beneaththe lake was sufficient to reduce 2 milliequiva-lents of N 1/10,000 methylene blue dye atroom temperature, but the deeper samples didnot reduce 2 milliequivalents of dye. Theaverage temperature of the deeper parts of thebog below 10 feet was 10°C in August 1953.The hydrocarbon analysis of the sediment justbeneath the lake shows no appreciable variationfrom the other copropel samples (Table 4).

The present stability, however, would disap-pear if the water table were lowered so as todrain the bog. Removal of the neutralizinghumic acids and partial aeration of the bogwould result in an increase in bacteriologicaldecomposition, in evolution of C02) and inacidity of the bog. Growth of acid-formingSphagnum under partially aerated conditionswould also increase the acidity of the surfaceportions of the bog. The acids, called "sphag-nol", possibly phenols, (D. B. Lawrence, Dept.of Botany, University of Minnesota, personalcommunication), are formed by Sphagnum and

4 Birge and Juday developed the so-called bomb-calorimetry values used by ecologists, as follows:carbohydrate 4100 cal/gm, protein 5650 cal/gtn,fat 9450 cal/gm. The food-group populations ofindividual lakes as determined in gm/m2 dry weightare converted to cal/cm2 by use of factors rangingfrom .261 to .600 for various food-groups (Linde-man, 1941b, p. 661). This method differs from thatused by Roelofs (1944) who, for an index of pro-ductivity, compared plant yield in pounds per acreto nutrient content (P, K, Ca, and Fe) of thewater. Roelofs found that lake bottoms in Michiganconsisting of a mixture of organic matter (probablyas copropel) and marl were the most productive ofbenthonic plants—30 per cent higher than that ofmarl bottoms.

can lower the pH of the surface portions of thebog to 4 around the Sphagnum growth centers.In highmoor bogs the abundance of Sphagnummaintains high acidity in the peat accumula-tions even at depths of several feet, but inwetter lowmoor peats the Sphagnum acids areneutralized or diluted at a depth of only a fewinches. According to Lawrence, the Sphagnumgrowth centers of Cedar Creek Bog form littlethin islands of low pH in the otherwise some-what alkaline bog.

The iron-rich marl at the base of the bog ishighly unstable under atmospheric conditions.The iron oxidizes and the sample changes fromblack to light yellowish brown when dried atroom temperature. The sample from 35-36 feetat station 2 contained 15.63 per cent total iron(Table 4) which appears to be siderite ("peatsiderite"), but some of it may be ferrous sulfidehydrate. The Eh of this material measured atroom temperature is poorly poised but givesthe strongest reducing intensity of any of thesamples; the total bacterial activity, however,is not great, as only one milliequivalent ofN/10,000 methylene blue dye was reduced bythe sediment. The pH, despite the high marlcontent, was only slightly alkaline, perhapsowing to the sulfur and iron compounds, and itvaried owing to poor buffering.

SUCCESSION IN THE BOG

The following is a modification of Lindeman's(1941a) discussion of the development of thebog. The origin of the lowermost sideritic,copropelic, marl layers of the deposit is not en-tirely clear. The organic matter, which musthave been derived principally from phytoplank-ton, yielded relatively small amounts of paraffi-nic and moderate to large amounts of aromatichydrocarbons (Table 3). The high concentra-tion of siderite in the basal layers suggests thatthere was no well-developed or consistent over-turn of the lake waters; otherwise much of theiron, in absence of high organic content, wouldbe oxidized and precipitated as limonite(Ruttner, 1953, p. 76). On the other hand, aconsiderable amount of the iron may have beenintroduced by ground water. Maintenance of alow Oz concentration in the bottom waters re-sults in the accumulation of iron carbonate in




the bottom sediments, especially in cold waterlakes of Order 1 type (Welch, 1952, p. 63) andin the meromictic type (Thienemann, 1915).In the latter a semipermanent saline hypolim-nion may form beneath the temperaturehypolimnion and prevent complete overturn.

which in turn passes into a cedar forest con-taining Sphagnum hummocks. In the middle ofthe bog marl deposition continued almost up tothe bottom of the present pond.

A hypothetical curve of the rate of depositionwithin this bog is given in Figure 5.

olc

1on"E01

0)en"ocg"o-3

§20

^

YearsWOO 7500 5000 2500 0

l'/750yrs(l'/540yrs.)

I'/ISOyrs.(l'/l30yrs)

l'/360yrs.

^-- forest a-~ -^sphagnum peat

^ ̂ grading to sedge peat^x

/

/

/ Sedge peat grading to/ eutrophic copropel

1

11 Organic marl grading to sideritic marl' 14

C date ±8000 years

FIGURE 5.—HYPOTHETICAL CURVE OF RATE OF DEPOSITION BENEATH STATION 1, CEDAR CREEK BOGFigures in parentheses indicate deposition rate when moisture content of peat is reduced to that of

marl (65%).

A typical eutrophic phase of the marl-form-ing type set in above a depth of approximately25 feet. This was marked by rapid deposition ofphytoplankton under partly reducing condi-tions to form a mixture of copropel, sapropel,and marl in the epilimnion zone. The thin layerof dark-brown copropel (Fig. 2) may representsome climatic variation in which the depositionof coprogenic material exceeded that of marl(Lindeman, 1941a, p. 109). This copropel zonemay represent temporary deepening of the lakecaused by a rise in water table and resulting indevelopment of a hypolimnion where marl for-mation was inhibited. The hydrocarbons formedin the marly portion of the bog were derivedprincipally from finely particulate phyto- andzooplankton, modified by activity of benthonicworms, larvae, and crustaceans.

Above a depth of 11 feet at station 1 theeutrophic lake gradually passed into a bog, theplants of which encroached upward and out-ward until at present there remains only a smallpond, surrounded by a quaking sedge bog

TABLE 5.—APPROXIMATE TONNAGES PER ACREFOOT OF VARIOUS EXTRACTABLE MATERIALS

IN CEDAR CREEK BOG

Peat, copropeland sapropel

Marl

Totallipoids

86

26

Totalhydro-carbons

14

4

Totalasphalts

18

7

Polarcom-

pounds

56

15

QUANTITY OP EXTRACTABLE MATERIAL

Table 5 gives the approximate amounts oflipoids, hydrocarbons, asphalts, and polar-oxygenated extractables in the peat and in themarl, based on averages of figures given inTable 3, and using values of 68 lbs./ft.3 for thepeat and 92 lbs./ft.3 for the marl. These arebased on the figures for moisture content givenin Table 2, rounded off to the nearest ton. Aspecific gravity of 0.9 is assumed for the lipoidmaterials.



CONCLUSION 1197

CONCLUSION

Cedar Creek Bog contains the following de-posits and associated lipoids in ascending se-quence: (1) thin basal sidenti marl havingabout 1.5 per cent lipoids: (2) copiopelic andsapropelic marl averaging 1.5 per cent lipoids,more than 30 feet thick in the middle of thedeposit; (3) fine textured copropel and sapropelaveraging 6.5 per cent lipoids and up to 10 feetthick in a zone peripheral to the thickest marl;(4) sedge peat and overlying forest peat aver-aging 6.3 per cent lipoids and thickest in a beltperipheral to that having the thickest copropeland sapropel. The highest per cent of lipoids inindividual samples at station 1 was found at4-5 feet where pollen is abundant, and at 10-11feet just above the marl.

The 10-11 foot sample also contains thehighest per cent of the saturated hydrocarbonfraction of the lipoids. The sample containingthe largest aromatic fraction is at 8-9 feet atstation 1 in copropel and sapropel which other-wise is similar to the adjacent material. Thefine textured copropel and sapropel containsslightly more polar organic substances otherthan hydrocarbons and asphalts.

Although knowledge of source and process ofhydrocarbon formation is incomplete, the evi-dence definitely points toward a contempora-neous accumulation of the hydrocarbons, otherlipoids and bog sediments. An important stepin the genesis and liberation of hydrocarbonsfrom the plants may be the maceration andpartial breakdown of the larger molecules inthe copropel zone by the action of browsingand predatory snails, worms, and many ar-thropods. The environment of the hydrocarbonaccumulation here is mildly alkaline with pHrange from 7.1 to 7.8, low intensity of oxidationpotential in the stable parts of the bog (+125to +445 mv), and slight reducing intensity be-neath the lake in the more active parts of thebog ( + 167 to +299 mv), with relatively smallreducing capacity in the deeper parts.

REFERENCES CITED

Barr, K. W., Morton, F., and Richards, A. R., 1943,Application of chemical analysis to problemsof petroleum geology: Am. Assoc. PetroleumGeologists Bull., v. 27, p. 1595-1617, figs. 1-11.

Buell, M. F., and H. F., 1941, Surface level fluc-

tuations in Cedar Creek Bog, Minnesota:Ecology, v. 22, p. 317-321.

Conant, J. B., and Blatt, A. H., 1947, The chem-istry of organic compounds: N. Y., MacMillanCo., p. 1-665.

Davis, J. B., and Squires, R. M., 1954, Detection ofmicrobially produced gaseous hydrocarbonsother than methane: Science, v. 119, p. 381-82.

Erdtman, H., 1943, in Erdtman, G., An introduc-tion to pollen analysis: Waltham, ChronicaBotanica Co., p. 1-239.

Flint, R. F., and Deevey, E. S., Jr., 1951, Radio-carbon dating of late Pleistocene events: Am.Jour. Sci., v. 249, p. 257-300.

Kolvoort, E. C. H., 1938, Crystal twins of normalC24H6o and the influence of phase transitions ontheir orientation: Jour. Inst. Petroleum Tech-nology, v. 24, p. 338-347.

Liebmann, H., 1950, Zur Biologie der Methanbak-terian: Gesundheits-Ingenieur, v. 71, p. 14-22, 56-59.

Lindeman, R. L., 1941a, The developmental historyof Cedar Creek Bog, Minnesota: Am. MidlandNaturalist, v. 25, p. 101-112, figs. 1-7.

Lindeman, R. L., 1941b, Seasonal food-cycledynamics in a senescent lake: Am. MidlandNaturalist, v. 26, p. 636-673, figs. 1-5.

1942a, Experimental simulation of winteranaerobiosis in a senescent lake: Ecology, v.23, p. 1-13, 1 fig.1942b, The trophic-dynamic aspect of ecology:

Ecology, v. 23, p. 399-418, figs. 1-3.Newmann, L. M., Bass, N. W., Ginter, R. L.,

Manney, S. F., Rynicker, C., and Smith, H.M., 1941, Relationship of crude oils andstratigraphy in parts of Oklahoma and Kansas:Am. Assoc. Petroleum Geologists Bull., v. 25,p. 1801-1809, figs. 1-3.

Nevin, C., 1945, Origin of petroleum—a method ofapproach: Am. Assoc. Petroleum GeologistsBull., v. 29, p. 285-288, 1 fig.

Roelofs, E. W., 1944, Water soils in relation to lakeproductivity: Mich. State College Agr. Exp.Sta., Tech. Bull. 190, p. 1-31, figs. 1-4.

Ruttner, F., 1953, Fundamentals of limnology(translated by D. G. Frey and F. E. Frey),Toronto, Univ. of Toronto Press, p. 1-242.

Sachanen, A. N., 1945, The chemical constituentsof petroleum: N. Y., Reinhold Pub. Corp.,p. 1-451.

Schreiner, O., and Shorey, E. C., 1911, Paraffinhydrocarbons in soils: Am. Chem. Soc. Jour.,v. 33, p. 81-83.

Smith, P. V., Jr., 1952, The occurrence of hydro-carbons in Recent sediments from the Gulf ofMexico: Science, v. 116, no. 3017, p. 437-439.1954, Studies on origin of petroleum: Occur-

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Thienemann, A., 1915, Das Ulmener Maar: Fest-schr. medeinish naturf. Gesellschaft, Minister(not seen by writers).

Titow, N., 1932, Uber die Bitumina des Sphagnum-torfes: Brennstoff-Chemie, v. 13, p. 266-269.

Tulsa Geological Society Research Committee,1947, Relationship of crude oils and stratigra-phy in parts of Oklahoma and Kansas: Am.Assoc. Petroleum Geologists Bull., v. 31, p.92-148, figs. 1-30.



11Q8 SWAIN AND PROKOPOVICH—LIPOID SUBSTANCES

Waksman, S. A., 1936, Humus: Baltimore, Williams marine sediments: Am. Assoc. Petroleumand Wilkins Co., 494 pages. Geologists Bull., v. 30, p. 477-513, figs. 1-5.

Welch, P. S, 1952, Limnology: 2nd ed, N. Y., UNIVERSITY OF MINNESOTA, MINNEAPOLIS, MINN.McGraw-Hill Book Co., Inc., p. 1-538. MANUSCRIPT RECEIVED BY THE SECRETARY OF THE

Zobell, C. E., 1946, Studies on redox potential of SOCIETY, MARCH 30, 1954



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