BULLETIN OF T H E AMERICAN ASSOCIATION OF PETROLEUM GEOLOGISTS

VOL. 40. NO. 5 (MAY. 1956), PP. 897-908, 4 FIGS

GEOCHEMICAL INVESTIGATION OF CRUDE OILS'

LAWRENCE C. BONHAM'
La Habra, California

ABSTRACT
A spectrochemical study was made of 66 crude-oil samples from different parts of the United
States to investigate the geologic significance of trace metals in oils. Among the oils analyzed, those
from some basins contain distinctively different trace-metal suites, but oils from basins of similar age
and environment do not show characteristic differences. A detailed study was made of Lower Pennsyl-
vanian oils from the Seminole area, Oklahoma. The trace-element content of these oils did not serve
to correlate producing strata from pool to pool or to differentiate producing strata. The areal distribu-
tion of vanadium and nickel concentrations in the Seminole area, however, is closely related to
paleogeographic trends: the concentrations are greatest near the shoreline and decrease basinward.
The decrease in concentration may be attributed to adsorption of the polar metal-bearing organic
constituents during migration or to different metal contents of oils that originated in different parts
of the basin.

INTRODUCTION

For a number of years geologists have been aware of the significance of the
minor constituents of earth materials. Geological literature contains the results of
many investigations in which trace constituents were used as indicators of envi-
ronmental conditions during the genesis of rocks or mineral deposits and as means
of identifying geological units. Although the occurrence of traces of metallic
elements, such as vanadium and nickel, in petroleum and related substances, is
well known, only recently have these minor constituents received much attention
(Erickson, Myers, and Horr, 1954; Hodgson, 1954); and relatively few attempts
have been made to use trace-metal data for the solution of problems in petroleum
geology.
The primary purpose of this study was to investigate apphcations of the
trace-metal content of crude oils for geological purposes. Before this purpose could
be accompHshed, it was necessary to develop methods of spectrographic analysis
to detect the presence and determine the concentration of metals in a representa-
tive group of crude oils. In addition, studies were made to determine the manner
of occurrence of the trace metals in petroleum so that the constituents related to
oil genesis could be differentiated from those added during migration and accu-
mulation.
The data obtained from the analyses were used to evaluate the feasibility of

' Contribution No. 174, Washington University, Department of Geology and Geological Engi-
neering, St. Louis, Missouri. Manuscript received, August 30, 1955.
' California Research Corporation.
This paper is from a dissertation submitted in partial fulfillment of the requirements for the
degree of Doctor of Philosophy at Washington University, St. Louis, Missouri, June, 1950. This in-
vestigation was made possible by a research grant to Washington University from the Standard Oil
Development Company. Grateful acknowledgment is made for this assistance and for the cooperation
of the Standard Oil Development Company and the Carter Oil Company in furnishing samples,
geological information, and advice during the progress of the work. The writer is indebted to Carl
Tolman, A. F. Frederickson, and other members of the geology and chemistry departments at Wash-
ington University for guidance throughout the investigation. W. S. Lytic, of the Pennsvlvania Geo-
logical Survey, provided several oil samples.

897
898 LAWRENCE C. BON HAM

(i) recognizing crude oils from different basins or provinces, (2) correlating crude
oils from different pools, (3) recognizing crude oils from different producing strata
in the same area, (4) establishing environmental conditions during oil genesis,
and (s) tracing routes of oil migration.

METHODS OF ANALYSIS

Spectrographic analysis was used in this investigation, as in most trace-

component studies, because of the low concentration of the constituents. Metallic
elements were determined by emission spectroscopy, and the metal-bearing com-
pounds were identified by means of absorption spectrometry.
A special spectrographic technique was developed for the analysis of metals in
oils. The crude oils, with added cobalt internal standard, were ashed directly in
graphite electrodes. The cathode layer method of excitation (Strock, 1936) was
used to enhance the intensity of spectral lines, and the samples were arced in a
helium-oxygen atmosphere to reduce background intensity and to suppress band
spectra.
In the investigation of the nature of the metal-bearing components of crude
oils, the Institute of Petroleum methods (1948) were used for separation of
asphaltic constituents, conventional distillation was used to separate different
boiUng-range fractions, and the technique outlined by Treibs (1934) was used
for extraction of porphyrin compounds. The acid extracts were analyzed in the
3,500-7,000 Angstrom range by means of a quartz absorption spectrometer.

SAMPLE DATA

A group of oil samples from strata ranging in age from Ordovician to Eocene
was assembled from different parts of the United States to investigate the dif-
ferences in trace-metal suites of oils from different basins. A suite of 45 samples
was obtained from the Lower Pennsylvanian sands of the Seminole, Oklahoma,
area for the studies of crude-oil distinction, pool correlation, environment during
origin, and migration route. Data concerning all samples are listed in Tables II
and III. All of the oils sampled are believed to be of marine origin except the two
Eocene samples, which are lacustrine.
The Seminole area is in east-central Oklahoma on the northwestern margin
of the McAlester-Arkansas basin (Fig. i). The basin is bounded by the Ozark
dome on the northeast, the Ouachita folded and faulted belt on the southeast,
the Arbuckle Mountains on the south, and the Hun ton arch on the west. The
Lower Pennsylvanian strata in the Seminole area are listed in Table I. Oil samples
were obtained from various sand members of the Morrow series and the Atoka,
McAlester, and Boggy formations.
The Lower Pennsylvanian rocks of this area consist of alternating shales and
sands with a few limestones and coal beds. The bulk of the sediments was derived
from a low landmass bounding the basin on the northwest, the shorelines of which
trended northeast-southwest (Levorsen, 1931, 1933). The shale sections appear
 GEOCHEMICAL INVESTIGATION OF CRUDE OILS 899

TABLE I. LOWER PENNSYLVANIAN STRATA OF SEMINOLE AREA, OKLAHOMA

Series Group Formation Member

Calvin
Senora
Stuart
Thurman
Boggy*
Savanna
Des Moines
Upper Booch sand*
McAl ester Middle Booch sand*
Lower Booch sand*

Atoka Gilcrease sand*

Wapanucka
Morrow Morrow Morrow shale
Union Valley
Cromwell Cromwell sand*

Strata from which oil samples were obtained.

on the edge of the Hunton arch and thicken markedly toward the basin area on
the east. The limestones appear farther east from the old shoreline and also
thicken basin ward. The sandstones of the Seminole area represent sporadic, near-
shore deposits extending for varying distances into the basin.
Structural movement in the basin occurred during and after deposition, as
shown by the more pronounced structural features of the older formations. Wil-
son (1937) calls attention to several folds and faults which decrease in intensity

K A N S A S J""
M I S S O U R I

OZARK DOME

(/ \
O K L A H O M A :^^;J(:4

I A R K A N S A S

OUACHira RE6I0N

T E X A S
LOUISIANA

FIG. I.Index map showing Seminole area, Oklahoma, and

related structural features.
900 LAWRENCE C. BON HAM

up through the Lower Pennsylvanian formations. The original easterly dips of

the strata were reversed after deposition; the producing formations which are
2,000-3,000 feet deep in the Seminole area crop out in the Muskogee area on the
east (Levorsen, 1933).
The oil pools of the Seminole area are arranged in northeasterly trending
belts (Fig. 2), which are marginal to the sedimentary basin and parallel with the
shorelines of the Lower Pennsylvanian seas. The locations of oil samples obtained
from the Seminole area are shown in Figure 2.

N. OKEMAH

OKFUSKEE COUNTY

29

#V/DLISTIN

SEMINOLE COUNTY

J IWEWOKA LAKE

^ I 4 1

' ri' (r?wE*ot

HUGHES COUNTY

W. HOLDENVILLE CREEK^ 3 o C ' ^ * " ' " ' 5 CORNER

^LITTLE RIVER
^^

FISH

ir'
r~V^^HA*KINS Sample
36 Locolion

( \ Oil Pool

FIG. 2.Map of Seminole area, Oklahoma, with locations from which oil
samples were obtained for spectrochemical analysis.
 GEOCHEMICAL INVESTIGATION OF CRUDE OILS 901

R E S U L T S OF SPECTROGRAPHIC ANALYSES

The results of the qualitative spectrographic analyses of 66 crude-oil samples

are summarized in Table II. In addition to the metals listed, calcium, silicon,
magnesium, aluminum, and sodium were detected in nearly all of the samples.
Although these elements may occur in oil in part as components of organic com-

TABLE II. RESULTS or QUALITATIVE SPECTROGRAPHIC ANALYSIS

Location No. of
Formation or Member Age V Cu N Fe Pb Mn Zn Cr Sr
Sampfei

Boggy L.Penn. Okla. I M W S T 0 0 0 0 0

Boocn L.Penn. Okla. IS T-S T - M W-S T 0 0 0 0 0
Gilcrease L.Penn. Okla. 6 W T M-S T 0 0 0 0 0
Cromwell L.Penn. Okla. 23 T-W T-W W-S T 0 0 0 0 0
Deese and Gibson L.Penn. Okla. 6 W-M T M T T 0 0 0 0
Viola Ordov. Okla. I T T S 0 0 0 0 0 0
Bromide Ordov. Okla. T-S T T-S T 0 0 0 0 0
Traverse a n d Dundee Devon. Mich. s2 T T W W 0 0 0 0 0
Wasatch Eocene Utah, W T S 0 0 0 0 0
Colo.
2
s
Newcastle Cret. Wyo. I T T M 0 0 0 0 0 0
Madison Miss. Wyo. I S T S T 0 0 0 0 0
Bradford Devon. Penn. 12 T T T M 0 0 0 0 0

Estimated ConceTUrattons
0 N o t detected
T Trace < o . I ppm.
W Weak 0 . 1-0.3 ppm.
M Moderate 0 . 3-1.0 ppm.
S Strong > i . 0 ppm.

plexes, the chances of contamination from minerals containing these common

elements are so great that spectrographic analysis is not a reliable method for
detection of such organic compounds. The results for samples from different pro-
ducing beds are not strictly comparable because of the range in the number of
samples available from each area. The analyses, however, illustrate some re-
gional differences in trace-metal suites of the various oils.
The results of the quantitative determination of vanadium, nickel, and cop-
per in 66 crude-oil samples are presented in Table III. Each value represents the
mean of triplicate analyses. Reproducibility studies indicate that the average
deviation from the mean of the triplicate values is approximately 4 per cent.
The three elements, vanadium, copper, and nickel, were selected for quanti-
tative studies because they are known to form metallo-organic compounds, such
as porphyrins, which may be indigenous to petroleum. Moreover, these metals,
relatively free from contamination difficulties, are the only ones which were de-
tected in a sufficient number of samples for inter-comparisons among the oils.

MANNER OF OCCURRENCE OF TRACE METALS IN CRUDE OILS

Deposits of asphaltic bitumens throughout the world contain metals such as
vanadium, nickel, and copper; in fact, some of these deposits such as the asphalts
in Peru (Wright, 1940) and the famed Mansfield Kupferschiefer in Germany
(Bateman, 1946) are rich enough to be mined as ores. Moreover, surprisingly
high vanadium and nickel concentrations have been observed in the flue dust
derived from the combustion of oil from certain sources (Thomas, 1938). These
902 LAWRENCE C. BON HAM

TABLE III. RESULTS OF QUANTITATIVE SPECTKOGRAPHIC ANALYSIS

Sample State Pool Formation Age Vanadium Copper Nickel

Number or Member PPm. ppm. ppm.
I Okla. Olympia Boggy L.Penn. .88 .10 2.40
2 Okla. Wewoka Lake Booch L.Penn. .33
95
3 Okla. Cheyarha Booch L.Penn. 32
.70
4 Okla. Cheyarha Booch L.Penn. 34 95
5 Okla. Hawkins Booch L.Penn. 2.10
. 8.50
6 Okla. Hawkins Booch L.Penn. .72
3-SO
7 Okla. Grief Creek Booch L.Penn. .10
.42
8 Okla. Bethel Booch L.Penn. 44 .11
9 Okla. Wewoka Lake Booch L.Penn. IS .26 .36
lo Okla. W. Wewoka Booch L.Penn. .14 .16 .42
II Okla. Wewoka Lake Booch L.Penn. .18
.27
12 Okla. Cheyarha Booch L.Penn. .21 .60 36
13 Okla. Cheyarha Booch L.Penn. .36
4.10
14 Okla. Booch L.Penn. .10
1.85
15 Okla. Grief Creek Booch L.Penn. .11
i6 Okla. W. Holdenville Booch L.Penn. 13
.46
17 Okla. Gilcrease L.Penn. . 30
i8 Okla. Gilcrease L.Penn. . 10
.36
19 Okla. Gilcrease L.Penn. .29
1-45
20 Okla. . Gilcrease L.Penn. .27
21 Okla. Cary Gilcrease L.Penn. IS
.6S
Okla. Gilcrease L.Penn.
.
21.
22 23
23 Okla. Cromwell Cromwell L.Penn. 23 .80
24 Okla. NE. Castle Ext. Cromwell L.Penn. .29
I-SO
25 Okla. Cromwell Cromwell L.Penn. .11
23
26 Okla. Cromwell Cromwell L.Penn. .10
. 23
27 Okla. N. Dill Cromwell L.Penn, .13
1-45
28 Okla. N. Okemah Cromwell L.Penn. .11
.70
2g Okla. Weleetka Cromwell L.Penn. .10
30 Okla. NW. Horns Cor. Cromwell L.Penn. .10
Okla. Cromwell L.Penn.
Horns
31 .10
32 Okla. Corner Cromwell L.Penn. .11 .70
33 Okla. Wewoka Cromwell L.Penn. IS
34 Okla. Dustin Cromwell L.Penn. .36
35 Okla. E. Seminole Cromwell L.Penn. .23 .11 .46
36 Okla. Cromwell Cromwell L.Penn, -17 23
37 Okla. Cromwell Cromwell L.Penn. .11 .27
38 Okla. Cromwell Cromwell L.Penn. .10
.42
39 Okla. Dill Cromwell L.Penn. -23
2.10
40 Okla. E. Yeager Cromwell L.Penn. 30 .12
41 Okla. NW. Horns Cor. Cromwell L.Penn.

Okla. Konawa Cromwell L.Penn. . 10

.
42 .65
43 Okla. Little River Cromwell L.Penn. 17 80 1.10
Okla. Fish Cromwell L.Penn. .
44 23
45 Okla. Horns Corner Cromwell L.Penn. 30
46 Okla. Katie Deese and Gibson Penn. .17
52
47 Okla. NE. Elmore Deese and Gibson Penn. IS
.60
48 Okla. NE. Elmore Deese and Gibson Penn. 17
.70
49 Okla. KaUe Deese and Gibson Penn. .48
. 1.60
SO Okla. Katie Deese and Gibson Penn. .29
1.00
51 Okla, Katie Deese and Gibson Penn. -24
1.00
Kan. . Viola Ordov. .
52 .95
53 Okla. SW. Maysville Bromide Ordov. 1.36 11 2.10
Okla. SW. Maysville Bromide Ordov. .25 1.10
54
Okla. Lindsay Bromide Ordov.
55
Okla. E. Lindsay Bromide Ordov. .
S6
Okla. E. Lindsay Bromide Ordov.

.10
57
Mich. Trent Traverse Devon.

5S
Mich. Dundee Devon. , 23

Wildcat .
59 23
60 Utah Wasatch Eocene .14
7^50
61 Colo. Seep Wasatch Eocene .24
4.70
Wyo. Skull Creek Newcastle Cretac. .42
62
63 Wyo. Madison Miss.
5.20 , 5^40
64 Penn.
Klondike Bradford Devon.
Penn. Klondike Bradford Devon.
65
66 Penn. Marshburg Bradford Devon,

.
indicates concentration of less than o.i ppm.

facts, together with observations of Shirey (1931) that high vanadium and nickel
concentrations are associated with asphalt-base crude oils, prompted a study of
the relationships between asphaltenes and trace-metal content of available oil
samples.
A rough correlation between asphalt content and vanadium-nickel concen-
tration in a group of oils is shown in Table IV.
 GEOCHEMICAL INVESTIGATION OF CRUDE OILS 903

TABLE IV

Sample No. Stratum ^^/^^^^^ - f^^^

6 Booch 0.43 0.72 3-5

7 Booch 0.02 O.IO .42
14 Booch 0.14 O.IO 1.8s
17 Gilcrease 0.00 O.IO 30
41 Cromwell 0.00 O.IO O.IO

Spectrographic analyses were made of fractions obtained by vacuum distilla-

tion of oil samples to 25oC. at 15 mm. pressure. Traces of copper were found in
several of the distillation fractions, but no vanadium or nickel was detected. An-
alysis of the distillation residue, however, suggests that the vanadium and nickel
were concentrated in the heavier fractions of the crude oil and were partitioned
between the asphaltene and non-asphaltene portions. The results of the anal-
yses of the distillation residue from sample No. 6 are shown in Table V.

TABLE V

Vanadium Nickel
ppm ppm
Distillation residue 2.8 10.8
Deasphalted residue 1.8 6.0
Asphaltenes 0.9 4.6

The metallo-organic compounds of vanadium, copper, and nickel known to

occur in organisms which may comprise the mother-substance of oil must be con-
sidered in the search for the source of trace metals in crude oils. These three ele-
ments are not among the classical ten elements considered essential for plant
growth (Rankama and Sahama, 1950), but they are micronutritional elements
which have characteristic physiological effects on plants, and have been reported
in many spectrographic analyses of plant material. In contrast to plants, animals
apparently concentrate only a few trace elements; but, significantly, copper and
vanadium are among these elements. Hemocyanin, a copper porphyrin, serves as
a respiratory pigment in some of the lower animals such as the crustaceans. Sig-
nificant amounts of vanadium are concentrated from sea water by the ascidians,
some holothurians, and a few gastropods. In the ascidians, the vanadium is con-
tained in a blood pigment, but the function of vanadium in the other organisms
is not clear (Vinogradov, 1953). Thus it appears that porphyrins and related
substances are likely carriers of petroleum trace elements.
Porphyrin is a term used for all ring structures derived from the fundamental
porphin ring, which is a planar arrangement of four conjugated pyrrole groups
linked by methenyl bridges. Porphyrins with a metal ion in the center of the ring
possess properties of great physiological significance. The iron porphyrins, or
hemo compounds, are constituents of hemoglobin in the blood of vertebrates
904 LAWRENCE C. BON HA -

where they act as oxygen carriers. Chlorophyll contains a magnesium porphyrin,

which serves as a catalyst in the removal of oxygen from water (Van Niel, 1941).
Metal ions incorporated in the porphin ring coordinate with the four pyrrole
nitrogen atoms. In addition, the metal may coordinate with other oxygen- or
nitrogen-containing groups such as hydroxyl, water, ammonia, or pyridene
above or below the plane of the porphin ring. The possible hydroxyl coordination
suggests a mechanism by means of which porphyrins can be adsorbed on the
basal layers of clay minerals by coordination with the hydroxyl ions of the clays.
Chlorophyll and hemoglobin porphyrins were first discovered in asphaltic
petroleum by Treibs (1934, 193s), who also extracted a complex vanadium por-
phyrin from several oils from different parts of the world. The extraction method
described by Treibs was used for treatment of two oil samples in this study.
Table VI lists peaks observed in the absorption spectra of extracts from each
sample, together with known absorption peaks of a porphyrin in acid solution.

TABLE VI

Wave Length (Angstroms)

4,000 S.Soo S,88o

Porphyrin in acid solution Strong Moderate Weak

Sample No. 5 (Booch) Weak Weak Weak
Sample No. 63 (Madison) Strong Weak Weak

INTERPRETATION OF RESULTS
The provincial character of the trace-metal suite in oils from different areas
is shown by an examination of the results of the qualitative and quantitative
spectrographic analyses. Lower Pennsylvanian oils from the Seminole, Okla-
homa, area contain small to moderate amounts of vanadium, copper, and nickel
and a trace of iron in contrast to Tertiary oils from the Uinta basin, which con-
tain small amounts of vanadium but relatively large amounts of nickel and iron
and appreciable manganese, zinc, chromium, and strontium. The Devonian oils
from Pennsylvania are characterized by small amounts of iron.
The contrasts in metal contents of oils from the Seminole area and other
Oklahoma oils from the Anadarko basin, however, are not striking and do not
serve to differentiate these two groups.
Some interesting interpretations can be made of the results of the Seminole
oil analyses. The range of vanadium and nickel content is not sufficient to dif-
ferentiate the various Lower Pennsylvanian producing strata, but the lateral
differences in metal concentrations show close relationships to paleogeographic
trends. Figures 3 and 4 are maps on which are contoured the concentration values
of vanadium and nickel. The contour pattern essentially parallels the production
trend of the Seminole area and the Lower Pennsylvanian shorelines; the metal
concentrations are greater along the northwestern margin of the basin where the
 GEOCHEMICAL INVESTIGATION OF CRUDE OILS 90s

LINCOL N
COUNTY

Vanadium concentrotion

Concentrolion less

FIG. 3.^Vanadium concentration in Lower Pennsylvanian oils from Seminole area, Oklahoma.

producing strata are thin and discontinuous. Basin ward the vanadium and nickel
contents decrease until they are no longer detectable by the methods used. Fingers
of high metal concentration that extend into the basin suggest deltaic patterns.
The evidence here presented shows that the metals occur in crude oils as
porphyrin compounds. In a sedimentary basin such as the one under considera-
tion, the highest concentration of organisms, both plant and animal, which could
supply these metal-bearing compounds would be found in the shallow, near-shore
environment. It may be postulated, therefore, that the oils in the western margin
9o6 LAWRENCE C. BON HAM

Nickel concentration

Concetltrolion
than 0.10 ppfP.

FIG. 4.Nickel concentration in Lower Pennsylvanian oils from Seminole area, Oklahoma.

of the Seminole area are near their original source and thus contain relatively
large concentrations of vanadium and nickel. The decreasing concentration of
vanadium and nickel in oils progressively farther from the shoreline suggests
that these oils have migrated successively greater distances from their original
source after reversal of dip in the area, and during migration the metallo-
organic components were removed by selective absorption on clays or other rock
constituents.
On the other hand, it may be postulated that the distribution of trace metals
 GEOCHEMICAL IXVESTIGATION OF CRUDE OILS 907

in the Seminole oils reflects the original metal content of the oils and that the de-
creasing concentration in the basin ward direction is due to different loci of origin.
The linear areas of high metal concentration that extend into the basin may repre-
sent oils with originally higher vanadium and nickel content, or they may be
areas in which the metal-bearing compounds were less effectively removed from
the oils during migration.
Regardless of the explanation for the trace-metal distribution, the relation-
ship to paleogeographic trends appears valid and useful.

CONCLUSIONS

It is concluded from this study that crude oils from certain different provinces
contain distinctive trace-metal suites, but that oils from basins of similar age
and environment may not show such characteristics. In the Seminole area, it
does not appear feasible to use the trace-element content of oils to correlate pro-
ducing strata from pool to pool or to differentiate producing strata, but these
applications are not precluded in other basins where the producing strata are
separated by a greater stratigraphic interval.
Vanadium and nickel are two elements indigenous to most crude oils and they
probably occur in porphyrin compounds derived from the organisms that pro-
vided the source materials for petroleum generation.
The areal distribution of vanadium and nickel concentration values in the
Seminole area is closely related to paleogeographic trends. The concentrations
are greatest near the ancient shorelines and decrease progressively basin ward. The
decrease in concentration may be attributed to adsorption of the polar metal-
bearing organic constituents by clay or other minerals in the rocks through which
the oil migrated, or the concentration gradient may be due to the differences in
metal content of oils that originated in different parts of the basin. Whatever
the cause, the trace metal pattern reflects the paleogeography; similar relation-
ships may be expected in other petroliferous areas.

REFERENCES CITED

BATEMAN, A . M . , 1946, Economic Mineral Deposits. Wiley, New York.

ERICKSON, R . L . , MYERS, A. T., AND HORR, C . A., 1954, "Association of Uranium and Other Metals
with Crude Oil, Asphalt, and Petroliferous Rock," Bull. Amer. Assoc. Petrol. Geol., Vol. 38,
p p . 2200-18.
HODGSON, G . W., 1954, "Vanadium, Nickel, and Iron Trace Metals in Crude Oils of Western Canada,"
ibid., Vol. 38, pp. 2537-54.
INSTITUTE or PETROLEUM, 1948, Standard Methods for Testing Petroleum and Its Products. Mansion
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LEVORSEN, A . I., 1931, "Pennsylvanian Overlap in the United States," Btdl. Amer. Assoc. Petrol.
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, 1933, "Studies in Paleogeography," ibid.. Vol. 17, pp. 1107-32.
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STROCK, L . W . , 1936, Spectrum Analysis with the Carbon Arc Cathode Layer. Adam Hilger, London.
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p. 1053. Oxford University Press, London.
9o8 LAWRENCE C. BONEAM
TREIBS, A., 1934, "Chlorophyll- und Haminderivate in bituminosen Gesteinen, Erdolen, Erdwachsen,
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1 193S) "Chlorophyll- und Haminderivate in bituminosen Gesteinen, Erdolen, Kohlen, Phos-
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VAN NIEL, C. B., 1941, "The Bacterial Photosynthesis," in Advances in Enzymology, Vol. i, p. 263.
Interscience, New York.
VINOGRADOV, A. P., 1953, Chemical Composition of Marine Organisms, translation by J. EFRON AND
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WILSON, C. W., JR., 1937, "Geology of the Muskogee-Porum District, Oklahoma," Oklahoma Geol.
Survey Bull. 57, p. 74.
WRIGHT, C. W., 1940, "Vanadium in Peru," Foreign Minerals Quar., Vol. 3, pp. 36-38.