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Chapter B 

Geochemistry of Minor and Trace Elements 

of 22 Core Samples from the Monterey 

Formation and Related Rocks in the 

Santa Maria Basin, California 

By JOEL S. LEVENTHAL 

U.S. GEOLOGICAL SURVEY BULL~TIN 1581 

STUDIES OF URANIUM CONTENT AND GEOCHEMISTRY OF THE 

MONTEREY FORMATION, CALIFORNIA 
DEPARTMENT OF THE INTERIOR 

DONALD PAU.L H.ODEL,.$ecretary. 

U.S. GEOLOGICAL SURVEY 

Dallas L. Peck, Director 

Any use of trade names in this report is for descriptive purposes only and 

does not imply endorsement by the U.S. Geological Survey 

UNITED STATES GOVERNMENT PRINTING OFFICE: 1989 

For sale by the 

Books and Open-File Reports Section 

U.S. Geological Survey 

Federal Center 

Box 25425 

Denver, CO 80225 

Ubrary of Congress Cataloging-In-Publication Data 

Leventhal, Joel S. 

Geochemistry of minor and trace elements of 22 core samples from the 

Monterey Formation and related rocks in the Santa Maria Basin, California. 

(Studies of uranium content and geochemistry of the Monterey Formation, 

California) (U.S. Geological Survey bulletin ; 1581-B) 

Bibliography: p. 

1. Geochemistry-California-Pacific Coast. 2. Trace 

elements-Analysis. 3. Monterey Formation (Calif.) I. Title. II. Series: 

Studies of uranium content and geochemistry of Monterey Formation. 

Ill. Series: U.S. Geological Survey bulletin; 1581-B. · 

QE75.89 no. 1581-B. 557.3 s [551.9'09794] 88-600385 

[QE515] 
CONTENTS 

Abstract Bl 

Introduction Bl 

Samples B2 

Analytical methods B3 

Results B3 

Statistical treatment B3 

Discussion B3 

Elements associated with the clay mineral fraction B3 

Elements in carbonate minerals B4 

Organic carbon and sulfur B4 

Association and abundance of trace elements BS 

Conclusion B6 

Acknowledgments BlO 

References cited BlO 

FIGURES 

1. Index map showing locations of 3 wells in the Santa Maria basin, 

Calif. B2 

2-16. Plot for 22 core samples from the Monterey Formation and related rocks: 

2. Ti versus Fe, correlation coefficient r=0.91 B8 

3. AI versus Sc, correlation coefficient r = 0.95 B8 

4. K versus Co, correlation coefficient r = 0.89 B8 

5. C03-C versus Ca, correlation coefficient r=0.77 B8 

6. Ca versus Sr, correlation coefficient r=0.80 B8 

7. C org versus S, correlation coefficient r=0.87 B8 

8. C org versus Cu, correlation coefficient r = 0.91 B9 

9. C org versus Ni, correlation coefficient r = 0.87 B9 

10. . S versus Ni, correlation coefficient r = 0.89 B9 

11. S versus Zn, correlation coefficient r=0.89 B9 

12. S versus Cr, correlation coefficient r ~ 0.87 B9 

13. C org versus V, correlation coefficient r= 0.70 B9 

14. C org versus Mo, correlation coefficient r=0.56 BlO 

15. C org versus U, correlation coefficient r= 0.73 BlO 

16. C org versus Cd, correlation coefficient r = 0.57 BlO 

TABLES 

1. Elemental abundance in 22 core samples from the Monterey Formation and 

related rocks, Santa Maria basin, California B4 

2. Mean abundance values and ranges of constituents of 22 core samples from 

the Monterey Formation and related rocks, Santa Maria basin, 

California B6 

3. Correlation coefficient matrix listing r values for analyses of 22 core samples 

from the Monterey Formation and related rocks B7 

Contents Ill 
STUDIES OF URANIUM CONTENT AND GEOCHEMISTRY OF THE MONTEREY FORMATION, CALIFORNIA 

Geochemistry of Minor and Trace Elements of 

22 Core Samples from the Monterey Formation and 

Related Rocks in the Santa Maria Basin, California 

By Joel S. Leventhal 

Abstract 

Twenty-two samples from the organic carbon rich Monterey Formation and related rocks have been analyzed for 

major, minor, and trace elements. Relative to averages 

reported for other organic-rich black shales, these samples 

are depleted in AI, K, Cu, La, Y, and Pb by about a factor of 

2. They are enriched by a factor of 2 in Mg, Na, organic C, 

Mn, Mo, Ni, and V and by a factor of 3 inCa and carbonate-e 

(C03-C). 

Statistical analysis, using correlation coefficients, was 

employed to determine affinity of trace elements. Certain 

trace elements (Sc, Co, Ga, Th, and Pb and rare earths-La, 

Ce, and Nd) are most associated with the major constituents . 

(AI, Na, K, Fe, and Ti) presumably in clay minerals. Mn and Sr 

are associated with the Ca and Mg carbonate phase. 

Organic carbon and sulfur are correlated in the Monterey Formation sediments as expected for marine organic 

carbon-rich sediments because of sulfate reduction by 

bacteria which utilize organic matter to form sulfide 

compounds. Trace metals-Ni, Cr, Cu, Zn, U, V, Mo, and 

Cd-are statistically associated with both the organic carbon 

and sulfur. However, some metals-Cd, V, Mo, and U-show 

greater statistical association with organic carbon than with 

sulfur. 

INTRODUCTION 

. Organic carbon rich mudstones often contain 

larger-than-average contents of metals. The metal 

content for 20 selected organic carbon-rich rock units h·as 

been summarized by Vine and Tourtelot (1970). 

However, their study did not include the Miocene MonManuscript approved for publication, August 11, 1988. 

terey Shale, which is more prominent as an oil-source 

rock than a metal-rich shale, and perhaps because it is 

not strictly a shale-containing smaller amounts of clay 

and greater amounts of biogenic silica (Bramlette, 1946; 

Isaacs, 1980). The Vine and Tourtelot (1970) results also 

do not include data on sulfur or phosphorus contents of 

the shales, due to the lack of an available analytical 

technique when their data was collected. Leventhal and 

Hosterman (1982) have reported detailed results for 

Devonian age shales from the Appalachian basin and 

showed that both organic carbon and sulfur are closely 

correlated with metals, indicating. that sulfur is an 

important element in black shales. 

The purpose of this report is to present new 

chemical data obtaine.d by modern instrumental 

techniques and to discuss the metal contents and their 

geochemical controls an~ affinities of the organic carbon 

rich mudstones of the Monterey Formation. Previous 

work on the Monterey Formation includes the classic 

study by Bramlette (1946) which reported chemical 

analyses for major elements. Major element chemistry 

data were given and discussed by Piper and Fowler 

(1979). Major and trace element (st:.miquantititive) 

chemistry was given by Isaacs (1980); however, only the 

major elements are discussed. A recent volume (edited 

by Garrison and Douglas, 1981) includes papers on the 

depositional environment ·of the Monterey Formation. 

·In the present study, a suite of 22 samples from 3 

wells from the Santa Maria basin (fig.1) was analyzed for 

major (except Si), minor (including S and P), and trace 

elements to determine the composition of the organicrich facies of the Monterey Formation. The·geology and 

stratigraphy of the Monterey Formation in general and 

also for these cores has been summarized by Durham 

(1987). In his report on the Monterey Formation, 

Geochemistry, 22 Core Samples, Monterey Formatlon,:Callfornla 81 
34° 

47' 

30" 

PACIFIC. 

OCEAN 

San Antonio 

Terrace 

5 MILES 

Union -<r 

Newlove 

51 well 

Figure 1. Index map showing locations of 3 wells in the Santa Maria basin, Calif. 

Durham was mainly concerned about ano:malous U 

contents and the source, mobility, and concentration of 

U. To further consider these questions, a geochemical 

study of the Monterey Formation organic carbon rich 

rocks (similar to that by Leventhal, Crock, and Malcolm, 

1981) was undertaken and is reported here. 

These 22 samples represent portions of three cores 

from the Santa Maria basin and are not necessarily 

representative of the whole Monterey Formation, which 

is quite heterogeneous. The trace elements in these 

samples are primary (syngenetic) as opposed to the 

higher uranium values that may be due to secondary 

(epigenetic) enrichment as reported by Durham (1987). 

82 Studies, Uranium Content and Geochemistry, California 

SAMPLES 

The samples (listed in table 1) are from the Union 

Newlove 51 well (1395-3509 ft depth1, sec 25, T. 9 N., R. 

34 W., samples 1-17), Union Dome 18 well (sec. 24, T. 9 

N.~ R. 34 W., 9868:-11,014 ft depth, samples .18-20) and 

the Union Bradley 1.well (sec. 26, T. 10 N., R. 34 W., 

4156 and 4849 ft depth, samples 21 and 22). 

1

0riginal depths from the drillers' log are given for 

identification purposes; 1 ft = 0.305 meters. 
The samples were all fine grained rocks, which are 

green, brown, gray, or dark gray in color and include 

siliceous mudstones, bedded cherts, and cherty shales. 

Some of the samples have laminations, which indicates a 

lack of infaunal burrowing and a very low oxygen or 

anoxic conditions during deposition. Six of the 22 

samples are from formations related to the Monterey 

Formation. In table 1, samples 1 and 2 are from the 

Sisquoc Formation, and samples 15, 16, and 17 are from 

the Point Sal Formatipn. Sample 18 is from the Sisquoc 

Formation. Some samples showed fractures with yellow 

staining, indicating subsequent (recent) oxidation and 

(or) chemical alteration during storage. 

ANALYTICAL METHODS 

Samples were described, and a representative 

portion was ground. Major, minor, and trace elements 

were determined by induction-coupled plasma 

spectroscopy (Taggart, Lichte, and Wahlberg, 1981) 

after acid digestion. Certain elements were at or below 

detection limits (in ppm, in parentheses) and are not 

listed in the results [Ag (2), As (10), Au (4), Be (1), Bi 

(10), Sn (4), Ta (40), U (40), Pr (10), Sm (10), Eu (2), 

Gd (10), Tb (20), Dy (4), Ho (4), Er (4), Yb (4)]. The 

following elements were not looked for: Si, B, W, Zr, Tm, 

and Lu. An important element, phosphorus, not reported 

by Vine and Tourtelot (1970), is reported for these rocks. 

The precision and accuracy are generally ± 10-15 

percent. 

Uranium was analyzed by the delayed neutron 

method (Millard, 1976). The precision and accuracy are 

generally ± 5 percent. Thorium results from delayed 

neutron analysis were not useful du~ to uranium 

interference. 

Total carbon was analyzed by LECO combustion, 

organic-carbon by combustion after acid leach, and 

sulfur by LECO combustion (Leventhal and Shaw, 

1980). The precision and ·accuracy are generally ±5 

percent. Several samples were analyzed for elemental 

sulfur-they showed less than 0.2 percent. Several 

samples were analyzed for non-pyrite, non-barite sulfur 

by acid leach (which removes soluble sulf~tes and 

sulfides); these values were also less than 0.2 percent. 

RESULTS 

The analytical results are shown in table 1. In 

several cases (indicated by an asterisk, *) the qualified 

(less than) values were changed to "real" values equal to 

one half the qualified value for purposes of statistical 

analysis and are listed as "real" values in table 1. Table 2 

shows arithimetic mean values and ranges for elemental 

constituents. 

STATISTICAL TREATMENT 

Correlation coefficients were run by the U.S. 

Geological Survey STATPAC statistical routine (VanTrump and Miesch, 1977) on the Data General 

Corporation ECLIPSE C/330 computer. The matrix 

array of correlation coefficient results is shown in table 3. 

For 22 sample pairs a coefficient of correlation (r) value 

of 0.54 or greater is significant at the 99 percent 

confidence level. Values of 0.49 and 0.42 are significant 

at the 98 and 95 percent confidence levels, respectively. 

However, visual inspection of scatter plots is necessary to 

ascertain the meaning of these results because a few high 

and low values (non-normal distribution) can r~sult in a 

high correlation coefficient that is not valid. 

DISCUSSION 

Major elements in sedimentary rocks, such as 

shale, occur as oxide minerals-mainly as silica (Si02 ) 

and clays (such as illite), and as carbonates. Sulfur occurs 

mainly in pyrite; organic carbon occurs in amorphous 

organic matter that coats grain surfaces as wen as filling 

interstices; and phosphorus occurs in phosphate. The 

trace elements are usually associated with one of these 

major or minor phases. 

Elements Associated With The 

Clay Mineral Fraction 

From the correlation coefficient (r) results (table 

3) the major elements AI, K, Fe, and Ti are all 

interrelated. For example, Fe versus Ti (fig. 2) is typical, 

showing a. high ( > 0.88) r value. Na is less highly 

correlated to these four elements (r <0.78). (These· 5 

elements are mainly contained in clay minerals.) 

Associated with these major elements are the trace 

elements Sc, Co, Ga, Th, Pb, La, Ce, Nd, and Nb. For 

example, Sc shows r of 0.84 or greater with the 5 major 

elements (table 3; fig. 3). In ~ddition, Co and Ga sh.ow r 

values in the range of 0.72 to 0.90 (for example, fig. 4, Co 

versus K) with the major elements. Th and Pb show low 

r values, only in the range 0.52 to 0.66 for Ti, AI, and K. 

The rare earth elements, La and Ce, show r values in the 

range 0.61 to 0.78 with AI, K, and Ti. Nd shows lower r 

values of 0.55. and 0.57 with Ti and K. The rare earth 

elements, La and Ce, are more closely correlated with 

each other (r = 0.87) than with the major elements a:s is to 

be expected. This is because· La, Ce, and Nd are in the 

Geochemistry, 22 Core Samples, Monterey Formation, California 83 
Table 1. Elemental abundance in 22 core samples from the 

[Values: %, indicates values given in weight percent; all other values are in parts per million; •, asterisk indicates a value which was less than 

No. Depth,ft Fe% Mg% Ca% Ti% Mn 

1 1395-1416 2.6 1.1 1.2 0.24 240 

2 1783-1798 3.2 1.1 1.3 .32 290 

3 1937-1955 1.8 .5 4.9 .1~ 160 

4 1980-2002 1.4 .84 5.9 .18 160 

5 . 1980-2002 1.5 .74 3.9 .19 170 

6 2018-2033 1.1 1.1 17.0 .12 300 

7 2119-2137 1.8 .81 2.3 .22 210 

8 2154-2165 1.5 .57 2.1 .20 130 

9 2240-2267 2.3 .96 6.0 .28 250 

10 2262-2276 2.4 .84 2.2 .28 210 

11 2435-2443 1.6 2.4 6.9 .18 200 

12 2625-2641 2.2 2.1 7.9 .22 220 

13 2660-2677 3.2 .91 4.3 .28 320 

14 2677-2696 2.5 1.7 3.0 .23 270 

15 3451-3460 3.2 1.8 2.1 .28 370 

16 3475-3491 2.8 1.8 2.5 .25 340 

17 3491-3509 3.4 1.8 1.5 .30 370 

18 9868-9875 3.2 1.2 1.3 .31 260 

19 10,105-10,114 1.2 .5 5.6 .14 150 

20 10,889-10,900 .97 5.0 12.0 .06 700 

21 4840-49 2.2 .63 12.0 .19 230 

22 4156~65 1.9 4'.9 9.5 .17 800 

rare earth element family (in fact all 3 are light rare 

earths),.and it is expected that their chemistry will be very 

similar. based on their identical valence electron 

configuration. Relative to average values reported for 

other organic carbon rich shales, the Monterey samples 

are depleted in AI and K and enriched in Si, Mg, and Na. 

Elements In Carbonate Minerals 

The elements Mg, Ca, Mn, · and Sr are often 

correlated with carbonate (C03-C); for example, .ca 

versus C03-C (fig. 5). The substitution of Mn and Sr in 

the carbonate lattice has been reported for sedimentary 

rocks (Leventhal and Hosterman, 1982). However, these 

results show Sr (fig. 6) associated with Ca (but not 

statistically .significantly with Mg), and Mn associated 

with Mg (not statistically significantly with Ca). Ba is not 

84 Studies, Uranium Content and Geochemistry, California 

Ba Cd Co Cr Cu La Mo Nb Ni Pb 

600 3 5 71 15 13 1* 6 31 2* 

620 4 7 85 19 19 4 8 40 10 

400 8 5 90 27 15 15 6 73 2* 

400 9 5 100 34 16 19 5 87 5 

150 8 4 100 28 16 18 5 66 5 

730 10 4 82 28 8 20 2* 70 2* 

310 15 5 130 45 20 23 9 100 8 

430 11 5 110 37 15 14 7 76 4 

460 14 8 190 67 23 23 8 130 8 

190 12 6 150 57 •24 28 9 100 5 

240 18 5 300 130 18 62 5 250 8 

330 10 6 270 83 18 34 6 200 7 

150 8 8 210 69 24 24 8 180 7 

270 7 7 170 41 6 18 5 130 7 

390 6 11 140 30 18 3 6 100 8 

410 7 9 130 29 19 8 6 89 7 

380 7 11 140 34 19 6 7 100 7 

340 4 6 91 18 20 1* 7 36 10 

290 16 3 110 45 15 66 4 89 5 

370 1* 2 52 10 7 6 2* 21 2* 

240 7 7 270 120 14 30 5 260 5 

290 9 4 71 21 17 24 8 51 9 

significantly correlated with any major constituents but 

does show a low r value (not statistically significant) with 

Sr and C03-C. Relative to average organic carbon rich 

:;hales, these Monterey Formation samples are enriched 

in C03-C and Mn. 

Organic Carbon and Sulfur 

Organic carbon and sulfur are highly correlated 

(r = 0.87) (fig. 7) as has been noted for modern marine 

sediments (Goldhaber anq Kaplan, 1974). This 

relationship is due to the sulf~te reduction by bacteria to 

produce sulfide and the f~ct that these bacteria use 

organic matter as a food soiuce. Because these bacteria 

can only metabolize a portion of the organic matter, the 

remaining organic carbon is preserved along with the 
Monterey Formation and related rocks, Santa Maria basin, California . . 

a qualified number that was changed to real values equal to one-half the qualified value for statistical analysis, for example, < 4 = 2*] 

No. Sc Sr v y Zn Al% Na% K% P% 

1 10 170 85 11 99 4.9 1.5 1.0 0.13 

2 12 250 100 14 73 6.6 1.8 1.4 .15 

3 9 310 180 12 140 3.5 1.2 .95 .13 

4 8 410 220 14 100 3.5 1.2 .89 .15 

5 7 330 210 15 77 3.7 1.3 .99 .25 

6 4 750 250 8 69 2.2 . 78 .62 . .15 

7 8 220 360 17 120 4.7 1.1 1.3 .18 

8. 7 210 250 13 130 4.1 1.1 .97 .11 

9 12 330 420 19 270 5.1 1.1 1.5 .26 

10 9 210 390 20 140 5 .. 2 1.2 1.5 .19 

11 8 210 600 25 310 3.3 .66 1.1 1.10 

12 7 260 510 27. 260 3.7 1.0 1.1 2.00 

13 11 210 360 29 300 5.7 1.1 1.6 1.50 

14 8 73 250 6 150 4.6 1.1 1.3 .13 

15 14 180 150 17 140 6.7 1.8 1.7 .10 

16 12 200 160 17 120 6.4 1.8 1.6 .10 

17 16 160 180 19 110 7.1 1.9 !.8 .11 

18 13 200 110 16 74 6.5 1.4 1.5 .32 

19 4 310 390 15 .96 2.7 .52 . 78 .19 

20 1* 300 260 6 86 1.·1 .37 .28 .11 

21 6 600 240 22 320 3.6 .87 1.2 1.40 

22 6 240 160 13 80 3.7 1.3 1.0 .21 

-. 

newly produced sulfide. If the proportion of 

metabolizable organic matter is constant, the 

sedimentation rate constant, and the amount and 

reactivity of iron constant-then the organic C versus S 

correlation is obtained. 

A variant on this organic carbon and sulfur 

relationship is the presence of a sulfur (non-zero) 

intercept of the linear least-squares-fit line (Leventhal, 

1983). This effect has been observed for sediments from 

the Black Sea and is interpreted to indicate the presence 

of the H2S laden water producing iron sulfide in the 

water column (as well as within the sediments). From the 

organic carbon and S data on the Monterey Formation 

(fig. 7), it appears that these samples fall into this 

category, which implies an H2S laden water above the 

sediments of the· Monterey Shale of the s·anta Maria 

basin that was an offshore basin at the time of deposition. 

The magnitude of the intercept is less than the Black Sea; 

thus, the H2S layer was thinner. than the Black Sea or 

more likely there were times of no H2S in the ove'rlying 

water but only anoxic conditions.· 

Ce Ga Th Nd u Org C%. S% 

20 9 2 9 2.8 0.86 0.70 

29 13 8 16 4.3 ~91 1. 27 

15 7 2* 12 11.6 3.45 1.60 

21 6 2* 10 14',5 4.15 1.53 

21 7 5 15 12.2 3.85 1.43 

9 2* 2* 13 8.1 4.53 1.00 

30 10 8 13 13.1 9.26 2.40 

20 7 5 15 13.1 7.47 2.20 

30 9 8 20 20.6 7.24 2.85 

37 10 9 21 15.8 6.40 2.80 

13 2* 6 17 32.2 12.7 3.80 

11 5 2* 21 16.5 9.48 3.90 

33 9 2* 27 14.0 7.85 4.70 

4 6 5 6 3.0 4.05 3.20 

25 11 6 16 3.8 2.22 1.05 

31 11 6 17 4.1 2.11 .90 

32 13 6 17 4.1 1.87 .92 

32 13 6 20 4.5 .74 .92 

14 6 5 9 17.1 2.13 1.50 

2* 2* 2* 10 2.9 1. 39 .43 

9 2* 5 13 ·13.4 14.4 5.06 

22 7 5 16 8.4 3.44 1.55 

Association and Abundance of 

Trace Elements 

co 3-c% 

0.38 

.22 

.62 

.98 

.59 

3.75 

.38 

.80 

.93 

.05 

2.29 

2.10 

.34 

1.35 

.53 

.63 

.23 

.40 

1.62 

5.50 

.87 

4.72 

Trace metals are associated with other trace metals 

in terms of highest correlation coefficients (r values); 

however, their geochemical control is with organic 

carbon and/or sulfur. Ni, Cr, Cu, and Zn are very highly 

correlated with Sand organic carbon (r >0.82). Figures 

8 through 12 show some of these relationships. V, Mo, U, 

and Cd are less highly correlated with organic carbon and 

S (figs. 13-16) than are Ni, Cr, Cu, and Zn. Phosphorus, 

which can form a phosphate mineral phase, such as 

apatite, that can contain certain metals, is correlated with 

Cr (0.81 ), Ni (0.80), Zn (0.80), Y (0.77), and Cu (0.76). 

From these statistical results it is not possible to 

determine if these elements are really associated with P, 

or if it is the association of P with organic C (r = 0.70) and 

S (0.80) that gives these high correlations. However, 

because these metals show higher r values with both C 

and· S than with P, only a fraction of these metals may 

reside in the phosphate minerals. 

Geochemistry, 22· Core Samples,. Monterey Formation, California BS 
Table 2. Mean abundance values and ranges of constituents of 22 core samples 

from the Monterey Formation and related r9cks, Santa Maria basin, California 

Major 

constituents Mean 

expressed as abundance Range an element [weight percent} 

A l. . . . . . . . . . . . . . 4 . 48 ( 1. 1 - 7. 1) 

Fe •....•.••••••• 2.18 (0.97 - 3.4) 

Mg .•.•..•.•••.•. 1.51 (0.50 - 5.0) 

Ca .••...•••••.•. 5.25 (1.2 - 17.0) 

Na .••..•••••..•. 1.19 (0.37 - 1.9) 

K .••.•.•.......• 1.19 (0.28 - 1.8) 

P ...•.•.....•••• .41 (0.11 - 2.0) 

Ti ..••.....••••. .22 (0.17 - • 31) 

orgC .•...••••••• 5.4 (0.74 - 14.4) 

C0 3-C ..•.••••••. 1.2 (0.22 - 4.7) 

s ... · ............ 2.1 (0.7 - 5.1) 

Trace Mean 

elements abundance Range 

(parts per million) 

Mn ••.•••••...•.• 298 

Ba .••••...••.••• 363 

Sr .••...•••••••. 279 

V .••.••••••.•••• 265 

Zn .•..••••...... 148 

Cr ..•••.••.••..• 139 

Ni ..•....•.••... 104 

. Cu .....• ~ ••..... 45 

Ce .•...•.•.....• 21 

La.· ••••••••••••• 17 

Nd •.... · •.•...... 15 

( 130 - 800) 

(150 - 730) 

(73 - 750) 

(85 - 600) 

(69 - 320) 

. (52 - 300) 

(21 - 260) 

(10 - 130) 

(<4 - 37) 

( 6 - 24 )-

(.6 - 27) 

· 1

organic matter is orgC x 1.3 

CONCLUSION 

Relative to the average chemical element values for 

black shales given by Vine and Tourtelot (1970), these 

Monterey Formation samples are enriched -in Mo, Ni, 

and V by about a factor of 2. However, they are also 

enriched in organic carbon by a factor of 2, and thus 

actually are rather similar to typical black shale in their 

B6 Studies,-Uranium Content and Geochemistry, California 

Mean 

abundance 

Major 

constituent 

expresse~ as oxides {weight percent) 

Al203 ...•......•..•...• 8.46 

Fe2o3 ..•••••...••...••. 3.12 

MgO ...•.•••••.••••••... 2.50 

CaO ..••......•......... 7.34 

Na2o ................... 1.60 

K20·············~······ 1.43 

P20s··················· .94 

Ti02··················· .37 

Organic Matter1 .••••.•. 7.0 

Carbonate ..•••.•..••... 6.0 

Trace Mean 

elements abundance Range 

(parts per mi 11 ion) 

Mo •....•.•... 20 (<2 - 66) 

y •••••••••••• 16 (6 - 29) 

Cd .•....•.•.. 8.8 ( <2 - 18) 

Co •.•.......• 6.0 (2 - 11) 

Nb ..•........ 6.1 (<4 - 9) 

Pb .......•... 6.0 (<4 - 10) 

Sc ••.....•.•• 8.7 (<2 - 16) 

Ga .••....•••. 7.6 (<4 - 13) 

Th •.••.•.•... 4.9 (<4 - 8) 

u •.• ~ •..•••.•• 11 (2.8 - 32.2) 

enrichment. These Monterey samples show less 

enrichment in all metals than some black shales, such as 

the Chattanooga Shale (Vine and Tourtelot, 1970; Leventhal and Hosterman, 1982), probably because of the 

greater sedimentation rate (Garrison and Douglas, 1981) 

of the Monterey -Formation and also because of the 

relatively larger silica content (Durham, 1987), both of 

which dilute the metal content. 
Table 3. Correlation coefficient matrix listing. r values for analyses of 22 core samples from the Monterey Formation and related rocks 

Fe Mg Ca Ti · Mn Ba Cd Co Cr Cu L~ Mo Nb N i Pb Sc Sr V Y Zn A 1 Na K P Ce Ga Th Nd U orgC 

Mg -- 1.0 

Ca -.61 . -- 1.0 

Ti . 91 -- -. 73 1.0 

Mn -- .91 -- -- 1.0 

Ba -- -- -- -- -- 1.0 

Cd -- -- -- -- -.41 -- 1.0 

Co .83 -- -.45 .77 -- -- -- 1.0 

Cr -- -- -- -- -- -.45 .45 -- 1.0 

Cu -- -- -- -- -- -.44 .56 -- .95 1.0 

La .51 -- -.48 .68 -- -- -- .45 -- -- 1.0 

C) Mo -.46 -- -- -- -- -.42 .81 -- .55 .68 -- 1.0 (II 

0 Nb . 57 -- -.64 . 75 -- -- -- .42 -- -- .80 -- 1.0 n Ni -- -- -- -- -- -.46 .47 -- .97 .96 -- .59 -- 1.0 ::r 

(II Pb -- -- -- .63 -- -- -- .47 -- -- .57 -- .58 -- 1.0 

3 Sc .88 -- -. 70 .91 -- -- -- .86 -- -- .61 -.43 .60 -- .54 1.0 

0 Sr -.50 -- .80 -.49 -- -- -- -- -- -- -- -- -.51 -- -.43 -.41 1.0 .. v -- -- -- -- -- -.40 .77 -- .71 . 74 -- .80 -- .67 -- -- -- 1.0 ~ y -- -- -- .42 -- -.48 -- .41 . 78 .72 . 75 .41 .44 . 73 .42 -- --. .56 1.0 1'\) Zn -- -- -·· -- -- -.40 -- -- .92 .90 -- .46 -- .92 -- -- ··- .65 .75 1.0 N 

0 Al .93 -- -. 75 .95 -- -- -- .84 -- -- .61 -.4.6 .68 -- .62 .95 -.53 -- -- -- 1.0 

0 Na .77 -- -.66 . 76 -- -- -- .72 -- -- .40 -.64 .53 -- .41 .84 -.41 -.62 . -- -- .87 1.0 ... K .88 -- -.64 .92 -- -- -- .89 -- -- . 70 -- . 70 -- .67 .90 -.47 -- .52 -- .93 . 72 1.0 CD 

en p -- -- -- -- -- -- -- -- .81 . 75 -- .43 -- .80 -- -- -- .56 . 77 .80 -- -- -- 1.0 

II) Ce .62 -- -.64 .77 -- -- -- .51 -- -- .87 -- .81 -- .50 . 74 -- -- .40 -- .78 .65 . 75 -- 1.0 

3 Ga .77 -- -.82 .85 -- -- -- .59 -- .43 .61 -.52 .71 -.40 .53 .83 -.57 -.44 -- -- .90 .83 . 76 -- .85 1.0 , Th -- -- -.45 .54 -- -- -- -- -- -- .52 .60 -- .62 .41 -- -- -- -- .52 -- .58 -- . 57 .51 1.0 

CD' Nd .49 -- -- .55 -- -- -- .41 .40 -- .80 -- .56 -- .47 .45 -- -- .77 .43 .46 -- .57 .49 .63 -- -- 1.0 $l u -- -- -- -- -.42 -- .84 -- .64 .77 -- .82 -- .65 -- -- -- .85 .58 .64 -- -.51 -- .47 -- -.41 -- -- 1.0 

3: orgC -- -- -- -- -- -.40 .57 -- .82 . 91 -- .56 -- .87 -- -- -- . 70 .60 .82 -- -.44 -- .70 -- -.49 -- -- . 73 1.0 0 s -- -- -- -- -- -.53 .44 -- .87 .87 -- .52 -- .89 -- -- -- .64 .67 .89 -- -- -- .80 -- -- -- -- .60 .87 1.0 ::::J 

.. co3-c -.59 .80 .77 -. 76 .71. -- -- -.56 -- -- -.55 -- -.56 -- -- -. 71 -- -- -- -- -. 71 -.58 -. 70 -- -.62 -.65 (II 

... 

(II 

'< 

., Fe Mg 0 

Ca Ti Mn Ba Cd Co Cr Cu La Mo Nb Ni Pb Sc Sr v y Zn Al Na K p Ce Ga Th Nd u orgC 

3 

a 

cr 

~ 

0 

!.. 

~ ... 

::::J 

i" 

m 

..... 
~ 3.0 w 

u 

a: 

~ 2.5 

1-

::J:: 

C) w 2.0 

~ 

~ 1.5 

z 

0 

!!: Lo 0 

o.aL-~~~--L_~-L~--L-~-L~~L_~_L~ 

0.04 0.1 0 0.20. 0.30 0.34 

TITANIUM, IN WEIGHT PERCENT 

Figure 2. Plot of Ti versus Fe, correlation coefficient r=0.91, 

for 22 core samples .from the Monterey Formation and related 

rocks listed in table 1. (Two samples plot at the solid symbol 

marked "2. •) 

z 16 

015 

::J 14 

= 13 ~ 12 

ffi 11 

0..10 

~ 9 

~ 8 Q.. 7 

~ 6. 

~ 5 ::> 4 

0 3 

z 2 

II I',,, I'''' I'''' I''' ·-r-· 

0 

t5 1 ~ o~~~~~~~~~~~~~~~~~w~~~ 

1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 

ALUMINUM. IN WEIGHT PERCENT 

Figure 3. Plot of AI versus Sc, correlation coefficient 

r= 0.95, for 22 core samples from · the Monterey 

Formation and related rocks listed in table 1. (Two 

samples plot at the solid symbol marked "2. •) 

0.50 0. 75 ' 1.0 1.25 1.5 1.75 

POTASSIUM, IN WEIGHT PERCENT 

Figure 4. Plot of K versus Co, correlation coefficient 

r=0.89, for 22 core samples from the Monterey Formation 

and related rocks listed in table 1. "(Two samples plot at the 

solid symbol marked "2. •) · 

88 · Studies,·UranJum Content and· Geochemistry, California . 

0.5 1.0 1.5 2.0 2.5 ·3.0 3.5 4.0 4.5 5.0 

CARBONATE-CARBON, IN WEIGHT PERCENT 

5.5 

Figure 5. Plot of C03-C versus Ca, correlation coefficient 

r=0.77, for 22 core samples from the Monterey Formation 

and related rocks listed in table 1. 

z 75o~~.,~~.,~~~~~TT~~~~~~~~ 

Q 700 ....J 

..J 

~ 600 a: 

w . 

Q.. 500 en 

1-

~ 400 Q.. 

~ 300 

~ ::> 200 

i= 

~ 100 a: so~~-~~~~~~~~~~~~~~~~~~ lii 0.0 2.5 5.0 7.5. ·10.0 12.5 15.0 17.5 

CALCIUM, IN WEIGHT PERCENT 

Figure 6. Plot of Ca versus. Sr, correlation coefficient 

r= 0.80, for 22 core samples from the Monterey Formation 

and related rocks listed in table 1. · 

5.00 

~ 4.50 w 

~ 4.00 

w 

Q.. 3.50 

1-a 3.00 

~ 2.50. 

~ 2.00 

~ 1.50 

~ 1.00 ::> 

en 0.50 

0 

0 

0 

0.00 c.........._,__~~'--"-.....___.-:-. L_.,__,__.__._...L._.__.__.__,c__.L_.__,_.___._L_.__...o.........a.___.__::] 

0.0 2.5 5.0 7.5 10.0 12.5 15.0 

ORGANIC CARBON, IN WEIGHT PERCENT 

Figur~ 7. Plot of C org ·versus S, correlation coefficient 

r= 0.87, for 22 .core samples from the Monterey Formation 

and related rocks listed in table 1. 
130 

~120 

::J 110 ...J 

~100 

I%: 90 w 

Q.. 80 

(/'J 70 ~ 

I%: 60 <( 

Q.. 50 

~ 40 

a: 

w 30 Q.. 

Q.. 20 

8 10 

0 

0.0 2.5 5.0 7.5 10.0 12.5 15.0 

ORGANIC CARBON. IN WEIGHT PERCENT 

Figure 8. Plot of C org versus Cu, correlation coefficient 

r= 0.91, for 22 core samples from the Monterey Formation 

and related rocks listed in table 1. 

275~~~~~~~~~~~~~~~~~-r~~ 

2 250 

3 225 ...J 

~ 200 

ffi 175 a.. 

(/'J 150 

~ 125 <( 

0..100 

~ 

J 75 w 

~ 50 

z 25 

o~~~~~~~~~~~~~~~~~~~~ 

0.0 2.5 5.0 7.5 10.0 12.5 15.0 

ORGANIC CARBON. IN WEIGHT PERCENT 

Figure 9. Plot of C org versus Ni, correlation coefficient 

r= 0.87, for 22 core samples from the Monterey Formation 

and related rocks listed in table 1. (Two samples plot at the 

solid symbol marked ·2. ·) 

25 

o~~~~~~~~~~~~~~~~~~~ 

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 

SULFUR. IN WEIGHT PERCENT 

Figure 10. Plot of S versus Ni, correlation coefficient 

r= 0.89, for 22 core samples from the Monterey Formation 

and related rocks listed in table 1. 

330~~rn~~~~~Tn"nTnorn~~no~~~ 

~ 300 

::J 

...J 

~ 250 

I%: 

w 

Q.. 200 (/'J 

~ 

~ 150; 

z 

~ 100 

N 

0 

5o~~~~~~~~LW~UL~~~~~Du~~ 

0.0 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 

SULFUR. IN WEIGHT PERCENT 

Figure 11. Plot of S versus Zn, correlation coefficient 

r= 0.89, for 22 core samples from the Monterey 

Formation and related rocks listed in. table 1. 

~3oo~~~~~~~~~~~~~~~~norn~n 

::J :::! 275 

~ 250 I%: 

~ 225 

(/'J 200 

~ <( 175 Q.. 

~ 150 

~ 125 

2100 

~ 75 

~ so~~~~~~~~~~~~~~~~~~~ 

u 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 

SULFUR. IN WEIGHT PERCENT 

Figure 12. Plot of S versus Cr, correlation coefficient 

r= 0.87,. for 22 core samples from the Monterey· Formation 

and related rocks listed in table 1. 

z 600 

D 

:::::i 550 ...J 

~ 500 

I%: 450 w 

Q.. 400 (/'J 

~ 350 

~ 300 

~ 250 

~ 200 ::::> 

c 150 

<( 

0 0 

z 100 

~ so~~~~~~~~~~~~~~~~~~~ 

0.0 2.5 5.0 7.5 , 0.0 12.5 15.0 

ORGANiC CARBON. IN WEIGHT PERCENT 

Figure 13. Plot of C org versus V, correlation coefficient 

r= 0. 70, for 22 core samples from the Monterey FormatiO'n 

and related rocks listed in table 1. 

Geochemistry, 22 Core Samples, Monterey .formation, California 89 
z 

070~~~~~~--~~~~~~~~~~~~ 

3 65 

~ 60 

a: 55 

~50 

(/) 45 

b: 40 

~ 35 

~ 30 

~ 25 

:::> 20 

~ 15 

~ 10 

~ 5 

o o~~-L~~~-L~~~~~~-L~~~-L~~ 

~ 0.0 2.5 5.0 7.5 10.0 12.5 15.0 

ORGANIC CARBON. IN WEIGHT PERCENT 

Figure 14. Plot of C org versus Mo, correlation coefficient 

r= 0.56, for 22 core samples from the Monterey Formation 

and related rocks listed in table 1. 

~ 30.0 

:::; 

...J 

~ 25.0 

a: 

w 

a.. 20.0 (/) 

b: 

~ 15.0 

z 

~ 10.0 

2 

~ 5.0 

a: 

:::> 0 

0.0 '--L.....J.._.J--'--L.....l-L~~~__._~__._~~l-L....L..-J'--'----'--'--'-~-' 

0.0 2.5 5.0 7.5 10.0 12.5 15.0 

ORGANIC CARBON, IN WEIGHT PERCENT 

Figure 15. · Plot of C org versus U, correlation coefficient 

r= 0. 73, for 22 core samples from the Monterey Formation and 

related rocks listed in table 1. 

Figure 16. Plot of C org versus Cd, correlation coefficient 

r = 0. 57, for 22 core samples from the Monterey ,Formation 

and related rocks listed in table 1. 

810 Studies, Uranium Content and Geochemistry, California 

ACKNOWLEDGMENTS 

The 22 core samples were obtained by C. M. Isaacs 

from Union Oil Co. and supplied by Dave Durham. 

Chemical analyses were done by Paul Briggs and 

Mark Stanton. 

Cheryl Adkisson and Ron Wahl assisted in 

operation of the ECLIPSE computer ·system used for 

statistical manipulations. 

REFERENCES CITED . 

Bramlette, M. N., 1946, Monterey Formation of California and 

the origin of its siliceous rocks: U.S. Geological Survey 

Professional Paper 212, 57 p. 

Durham, D. L., 1987, Uranium in the Monterey Formation of 

California: U.S. Geological Sutvey Bulletin 1581-A, 

29p. 

Garrison, R.' E., and Douglas,· R. G., editors, 198i, The 

Monterey Formation and related siliceous rocks of California: Society of Economic P::lleontologists and 

Mineralogists Symposium, Pacific Section, SEPM, Los 

Angeles, 374 p. 

Goldhaber, M. B., and Kaplan, I. R., 1974, The sulfur cycle, in 

E. Goldberg, editor, The Sea, v. 5, p. 569-655. . 

Isaacs, C. M., 1980, Diagenesis in the Monterey Formation 

examined laterally along the coast near Santa Barbara, 

Calif.: Ph.D. Thesis Stanford University, 329 p. and U.S. 

Geological Sutvey Open-File Report 8~6. 

Leventhal, J. S., 1983, An interpretation of carbon and sulfur 

relationships in Black Sea sediments as indicators of 

environment of deposition. Geochimica et Cosmochimica Acta, v. 47, p. 133-138. 

Leventhal, J. s:, Crock, J. G., and Malcolm, M. J., 1981, 

Geochemistry of trace elements and uranium in Devonian shales of the Appalachian basin: U.S. Geological 

Sutvey Open-File Report 81-778, 73 p. 

Leventhal, J. S., and Hosterman, J. W., 1982, Chemical and 

mineralogical analysis of Devonian black shale samples 

from Martin County, KY, Carroll and Washington 

Counties, OH, Wise County, VA and Overton County, 

TN, U.S.A.: Chemical Geology, v. 37, p. 239-264. 

Leventhal, J. S. and Shaw, V. E., 1980, Organic matter in 

Appalachian Devonian . black shale: Comparison of 

techniques to measure organic carbon: Jour. 

Sedimentary Petrology, v. 50, p. 77-81. 

Millard, H. T., Jr., 1976, Determination of uranium and 

thorium in USGS standard rocks by delayed neutron 

technique, in F:. Flanigan, editor, Descriptions and 

analyses of eight new USGS rock standards: U.S. 

Geological Sutvey Professional Paper 840, p. 61-66. 

Piper, D. Z. and Fowler,B. L., 1979, Sediment Chemistry, in H. 

E. Cook, editor, Geologic Studies of the Point 
Conception Well, southern Calif.: U.S. Geol. SurveyOpen File Report 79-1218, p. 97-108. 

Taggart, J. E., Lichte, F. E., and Wahlberg, J. S., 1981, Methods 

analysis using X-ray fluorescence and inductively coupled 

plasma spectroscopy, in P. Lipman and D. Mullineaux, 

editors, The 1980 Eruptions of Mount St. Helens, Washington: U.S. Geological Survey Professional Paper 1250, 

p. 683-692. 

VanTrump G., Jr., and Miesch A. T., 1977, U.S. Geological 

Survey RASS-STATPAC system for management and 

statistical reduction of geochemical data: Computer and 

Geoscience, v. 3, p. 475-488. 

Vine, J.D. and Tourtelot, E. B., 1970, Geochemistry of black 

shale deposits-A summary report: Economic Geology, 

v. 63, p. 253-272. 

Geochemistry, 22 Core Samples, Monterey Formation, California 811 

~U.S. GOVERNMENT PAINTING OFFICE 1989-673-047/86072 
Studies of Uranium Content 

and Geochemistry of the 

Monterey Formation, California 

This volume was published as separate chapters A and B 

U.S. GEOLOGICAL SURVEY BULLETIN 1581 
CONTENTS 

(A) Uranium in the Monterey Formation of California: by David L. Durham 

(B) Geochemistry of Minor and Trace Elements of 22 Core Samples from the 

Monterey Formation and Related Rocks in the Santa Maria Basin, California: by Joel S. Leventhal 
Peu-~odl~ctdl~$ 

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