Geochemistry of 

Bedrock Units in 

Missouri and Parts of 

Adjacent States 

By JON J. CONNOR and RICHARD J. EBENS 

GEOCHEMICAL SURVEY OF MISSOURI 

GEOLOGICAL SURVEY PROFES-SIONAL PAPER 954-F 

An examination of geochemical 

variability in rocks of 

Paleozoic and Precambrian ages 

UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON 1980 
UNITED STATES DEPARTMENT OF THE INTERIOR 

CECIL D. ANDRUS, Secretary 

GEOLOGICAL SURVEY 

H. William Menard, Director 

Library of Congress Cataloging in Publication Data 

Connor, Jon J. 

Geochemistry of bedrock units in Missouri and parts of adjacent states. 

(Geochemical survey of Missouri) 

(Geological Survey Professional Paper 954-F} 

Bibliography: p. 54 

Supt. Docs. no.; I 19.16: 954-F 

1. Rocks, Sedimentary. 2. Geology, Stratigraphic-Pre-Cambrian. 3. Geology, Stratigraphic-Paleozoic. 

4. Geochemistry-Missouri. 5. Geochemistry-Middle West. I. Ebens, Richard J., joint author. 

II. Title. III. Series. IV. Series: United States Geological Survey Professional Paper 954-F 

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

Washington, D.C. 20402 

Stock Number 024-001-03307-1 
CONTENTS 

Abstract ............................................... . 

Introduction ........................................... . 

Geologic setting ........................................ . 

Sampling design ........................................ . 

Precambrian rocks .................................. . 

Sauk sequence ...................................... . 

Tippecanoe sequence ................................ . 

Kaskaskia sequence ................................. . 

Pennsylvanian System .............................. . 

Analytical methods and data evaluation .................. . 

Page 

F1 

1 

2 

6 

7 

8 

14 

15 

17 

17 

Geochemical variability ................................. . 

Limestone and dolomite ............................. . 

Shale .............................................. . 

Sandstone and chert ................................ . 

Granite and rhyolite ................................ . 

Economic materials ................................. . 

Coal ........................................... . 

Lead-zinc-copper ore ............................ . 

Discussion ............................................. . 

References cited ........................................ . 

ILLUSTRATIONS 

Page 

F2'l 

21 

29 

33 

36 

37 

38 

42 

43 

54 

Page 

FIGURE 1. Diagram of major paths traveled in the natural migration of trace elements from rocks to humans. . . . . . . . . . . . . . . . . . . . . F2 

2. Map showing major geologic features in Missouri and adjacent States.............................................. 3 

3. Map showing generalized distribution of igneous rocks of Precambrian age in southeastern Missouri and distribution of 

sampling localities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 

4. Map showing sampling localities in the Sauk sequence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 

5. Map showing major lead mining and milling operations in southeastern Missouri and sampling localities.............. 14 

6. Map showing sampling localities in the Tippecanoe sequence....................................................... 15 

7. Map showing sampling localities in the Kaskaskia sequence....................................................... 16 

8. Map showing sampling localities in the Pennsylvanian System. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 

9. Diagram showing normative mineralogy of limestone and dolomite samples......................................... 21 

10. Diagram showing normative mineralogy of shale samples.......................................................... 29 

11. Diagram showing normative mineralogy of sandstone and chert samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33 

12. Diagram showing normative feldspar mineralogy of granite and rhyolite samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37 

13. Diagram showing normative mineralogy of coal samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39 

14. Graphs showing trace element concentrations in lithic bedrock units in Missouri and parts of adjacent States.......... 44 

15. Map showing location of cedar tree with unusually high concentrations of lead, zinc, and copper. . . . . . . . . . . . . . . . . . . . . . . 53 

TABLES 

Page 

TABLE 1. Distribution of terms in hierarchical statistical models used in sampling bedrock units in Missouri and adjacent States.. F8 

2. Sampling localities of Precambrian rocks in Missouri . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 

3. Sampling localities of stratified bedrock units in Missouri and adjacent States....................................... 10 

4. Analytical methods with lower limits of determination............................................................. 19 

5. Estimated variance of the analytical procedures for five rock types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 

6. Components of variance estimated for carbonate rocks of the Sauk sequence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 

7. Components of variance estimated for carbonate rocks of the Tippecanoe sequence................................... 23 

8. Components of variance estimated for carbonate rocks of the Kaskaskia sequence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 

9. Components of variance estimated for carbonate rocks of Pennsylvanian age. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 

III 
IV CONTENTS 

Page 

TABLE 10. Geochemical summary of rocks of the Sauk sequence............................................................... F 25 

11. Geochemical summary of rocks of the Tippecanoe sequence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 

12. Geochemical summary of rocks of the Kaskaskia sequence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 

13. Geochemical summary of rocks of Pennsylvanian age.............................................................. 28 

14. Components of variance estimated for shale of the Kaskaskia sequence.............................................. 30 

15. Components of variance estimated for shale of Pennsylvanian age. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31 

16. Geochemical medians for selected elements in areas of shale of the Kaskaskia sequence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 

17. Components of variance estimated for sandstone of the Roubidoux Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 

18. Components of variance estimated for chert of the Kaskaskia sequence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 

19. Components of variance estimated for sandstone of Pennsylvanian age.............................................. 35 

20. Components of variance estimated for igneous rocks of Precambrian age . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37 

21. Geochemical summary of igneous rocks of Precambrian age . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38 

22. Components of variance estimated for coal of Pennsylvanian age . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38 

23. Elements in samples of crushed and pulverized ore, lead, zinc, and copper concentrate and tailings from mining and 

milling operations in the Southeast Missouri Lead District . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40 
GEOCHEMICAL SURVEY OF MISSOURI 

GEOCHEMISTRY OF BEDROCK UNITS IN 

MISSOURI AND PARTS OF ADJACENT STATES 

By JON J. CONNOR and RICHARD J. EBENS 

ABSTRACT 

Distributions of elements were studied in 12 bedrock units of 

Precambrian and Paleozoic age in Missouri and adjacent parts of 

Kansas, Oklahoma, and Arkansas. This work constituted one part 

of a larger study aimed at characterizing the broad-scaled features 

of the geochemical landscape of Missouri. Rock units sampled were 

granite and rhyolite of Precambrian age; shale, dolomite, sandstone, 

and sulfide ore of the Sauk sequence (Cambrian to Early Ordovician 

in age); shale, carbonate, and sandstone of the Tippecanoe sequence 

(Middle Ordovician to Middle Devonian); shale, limestone, sandstone, and chert of the Kaskaskia sequence (Late Devonian to Late 

Mississippian); and shale, carbonate, sandstone, and coal of Pennsylvanian age. Eleven of these units were sampled according to 

hierarchical sampling schemes explicitly designed to estimate proportions of geochemical variation occurring at various geographic 

scales. 

The most important scale of geochemical variation is a local one 

that reflects a common tendency in sedimentary rocks for closely 

spaced samples to vary rather widely in their proportions of the 

common rock-forming minerals calcite, dolomite, quartz, and 

"clay." In fact, for many trace elements in many of the units 

studied, samples collected as much as 100 km apart are expected to 

vary in their geochemical properties little more than samples collected within a kilometer or two of each other. Regional geochemical 

variation reflects the contrasting lithology of the largely 

argillaceous units of Pennsylvanian age in the northern and western 

parts of the study area, and the largely calcareous units of the 

Kaskaskia, Tippecanoe, and Sauk sequences in the southern and 

eastern parts. 

Weaker geochemical distinctions that occur over intermediate 

geographic scales reflect correspondingly weak mineralogic variations within some of the lithic units. Limestone and sandstone 

samples from outcrops of Pennsylvanian age in northeastern 

Oklahoma generally have higher concentrations of trace elements 

than similar samples from northern Kansas and Missouri. Samples 

of carbonate rock from outcrops of the Kaskaskia sequence are 

more dolomitic in Missouri than in Arkansas, and dolomite samples 

from outcrops of the upper Sauk sequence tend to be slightly more 

argillic (and slightly higher in many trace elements) than dolomite 

samples from the lower Sauk (pre-Jefferson City rocks). 

The general control of rock geochemistry by lithology in the study 

area results in regional geochemical patterns largely indistinguishable from regional geologic patterns. This work has 

quantified such patterns in terms of the expected element concentrations to be found in the lithic units of the various regions of the 

study area. Therefore, geologic maps may be used in conjunction 

with the geochemical summaries given in this report to define "firstorder" estimates of the local geochemical background or of 

threshold values useful in characterizing unusual or "anomalous" 

samples. 

INTRODUCTION 

This report describes the results of a geochemical 

study of Precambrian and Paleozoic bedrock units of 

Missouri and adjacent States that was undertaken as 

part of a general survey of the geochemical environment in Missouri (Miesch, 1976; Tidball, 1976; Erdman 

and others, 1976a, b; Feder, 1979). The survey was 

conducted in cooperation with personnel of the Environmental Health Surveillance and Research Center 

of the University of Missouri in support of studies 

being made on the role of environmental geochemistry 

in health and disease. A preliminary description of the 

survey and its implications for epidemiological 

research was published by Connor and others (1972), 

and a general statement of goals and methods was 

given by Miesch (1976). Much of the work on which 

this paper is based has appeared in a series of progress 

reports (U.S. Geological Survey, 1972a-f, 1973) issued 

at intervals of 6 months during the life of the survey. 

Also, provisional geochemical summaries for most of 

the rock units discussed· in this report have appeared in 

a geochemical compilation of landscape units of the 

United States (Connor, Shacklette, and others, 1975). 

The role of trace elements in health and disease has 

been of interest to medical researchers for a long time, 

and an increasing public awareness of trace-element 

hazards in the environment has focused attention on 

the need for reliable data on the probable concentrations and ranges of many of these elements in ordinary 

environmental materials under natural conditions. 

Most such studies have concentrated on the presence 

of trace elements in air, potable water supplies, 

foodstuffs, and soils. Nevertheless, rocks constitute 

F1 
F2 GEOCHEMICAL SURVEY OF MISSOURI 

FIGURE I.-Diagram of major paths 

traveled in the natural migration of 

trace elements from rocks to humans 

(from Miesch, 1972). 

the ultimate source of elements in the human environment (fig. 1), and their chemical character commonly 

plays an important role in the local geochemical setting. Rock geochemistry may be especially important 

in areas where mining or related activity has disturbed 

the surface of the Earth (Connor and others, 1971; 

Ebens and others, 1973). 

We express our appreciation to many U.S. 

Geological Survey colleagues for their assistance in 

this study. A. T. Miesch conceived, initiated, and 

directed the geochemical survey as a whole. Josephine 

G. Boemgen assisted in computer processing of the 

resulting data. About 450 rock and mineral samples 

were analyzed in laboratories of the U.S. Geological 

Survey for nearly 60 chemical elements. The analysts 

who performed this work follow: A. J. Bartel, L. A. 

Bradley, Floyd W. Brown, Mike Brown, J. W. Budinsky, C. L. Burton, J. P. Cahill, J. I. Dinnin, E. J. 

Fennelly, W. H. Ficklin, L. D. Forshey, I. C. Frost, 

Johnnie Gardner, H. Kirschenbaum, Lorraine M. Lee, 

Violet M. Merritt, Leung Mei, H. T. Millard, Jr., 

Roosevelt Moore, Wayne Mountjoy, H. G. Neiman, 

D. R. Norton, R. L. Rahill, V. E. Shaw, G. D. Shipley, 

M. W. Solt, J. A. Thomas, J. H. Turner, R. L. Turner, 

J. S. Wahlberg, and T. L. Yager. Samples were 

prepared for analysis by John Moreland. 

We acknowledge with thanks the services and 

facilities provided by Dr. Carl J. Marienfeld and his 

associates of the Environmental Health Surveillance 

and Research Center, University of Missouri. Personnel of the Missouri Division of Geological Survey and 

Water Resources assisted us in this study in many 

ways; specifically, we are indebted to W. B. Howe, 

State Geologist; Larry Fellows, Assistant State 

Geologist; and Ira Satterthwaite, James Martin, 

Charles Robertson, v.nd Heywood Wharton for 

valuable discussions and for assistance in sampling. 

Special acknowledgment is due Peter Sweeny of 

Cominco American, Inc., James Davis of Missouri 

Lead Operating Company, Kenneth Larsen and Harold 

Krueger of Ozark Lead Company, and Paul Gerdemann of St. Joe Minerals Corporation for their kind 

assistance in obtaining samples of ore from southeast 

Missouri. Similar acknowledgment is due operators of 

many coal mines from which samples were obtained. 

GEOLOGIC SETTING 

The study area is situated near the south-central 

edge of the cratonic interior of the North American 

continent and is dominated structurally by the Ozark 

Uplift (fig. 2), a site of mild but repeated uplift since 

late Precambrian time (Snyder, 1968, p. 73). The area is 

underlain largely by stratified rocks of Paleozoic age 

whose deposition, for the most part, reflects the slow 

epeirogenic transgressions and regressions of continental seas. The highest area, both topographically 

and structurally, is the St. Francois Mountains area of 

southeastern Missouri, away from which the enclosing 

Paleozoic sediments dip rather gently. The area is 

bordered on the east by the Illinois Basin, on the 

southeast by the Mississippi Embayment, on the 

south by the Ouachita Mountains, on the southwest by 

the Anadarko Basin, on the west by the Nemaha 

Uplift, and on the northwest by the Forest City Basin. 

· The general distribution of major stratigraphic units 

examined in this work is shown in figure 2. In general, 

these units are readily distinguished in outcrop as they 

are stratigraphically bounded by major unconformities 

easily recognized in the field. More detailed distributions of map units are shown on the State geologic 

maps of Missouri (McCracken, 1961); Iowa (Iowa 

Geological Survey, 1969); Nebraska (Nebraska 

Geological Survey, 1950); Kansas (University of Kansas, 1964); Oklahoma (Miser, 1954), and Arkansas 

(Banner, 1929). A recent synthesis of the geological 

environment of Missouri can be found in Stout and 

Hoffman (1973). 

The succession of geologic formations in Missouri is 

described by Koenig (1961); the succession in Kansas 

is described by Merriam (1963). Except for a few 

distinctive formations (the St. Peter Sandstone, for example), individual units in general cannot be traced 

very far across the area of outcrop. Detailed Paleozoic 

nomenclature in the Illinois Basin bears little 

resemblance to Paleozoic nomenclature in eastern Kansas (Adkison, 1966). In addition, stratified rocks are 
41~77 96" 950 940 93" 920 910 roo 890 I ! I j \ ( J Jl ( \ "10:1 , /'.. I '( 1 ( I ID })_.;>' ollllNOJSF- ·11 . ll I 

i 

! 

35o , '' f' IVI\LANOMA __ I--- "'tj r (' •-1- ! ARKANSAS,,.#--f ..,.,, ~~v . ..-.i-bf j! { ... J- ! I 

0 100 200 KILOMETERS 

EXPLANATION 

~ Post-Pennsylvanian 

Pennsylvanian-Showing 

top of the Des Moinesian 

Series (-D-) 

- Kaskaskia sequence 

[2J Tippecanoe sequence 

~ Sauk se uence--SR. Roubi~oux Formation 

Precambrian 

96' 940 92' 

40'1 ·•~u~<>JV< ,- \. 

KANSAS 

"'~1\t..qo 

.S..q.s~..,.k"o 

Area of figure 2 

o1J>''f'..._ 

\)~~-\~-<; 

liB" 

FIGURE 2.-Generalized geology of Missouri and parts of adjacent States. Modified from King and Beikman (1974) and American Association of Petroleum Geologists (1966). 

to 

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:> 

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rJ) 

~ 

0 

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F4 GEOCHEMICAL SURVEY OF MISSOURI 

conventionally correlated on the basis of geologic age; 

and, commonly, where the age of a lithic interval 

changes lateraily, its name changes also. Because the 

geochemical survey was broad in scale, a broad-scale 

classification of the Paleozoic rocks, based largely on 

the sequences of Sloss (1963), was used. 

Outcrops of igneous rocks are generally restricted to 

southeast Missouri, where they consist of a thick sequence of felsitic flows and welded tuffs intruded by a 

granitic batholith (fig. 3). The age of these rocks is 

about 1500 m.y. (Bickford, 1976, p. 152; Bickford and 

Mose, 1975). Diabasic and basaltic dikes and sills have 

been locally intruded into both the felsites and 

granites, but they are of limited extent in outcrop and 

were not sampled in this work. 

The felsites are believed to have been extruded onto 

an eroded terrane of metamorphic and igneous rocks of 

early to middle Precambrian age similar to those 

presently exposed on the Canadian Shield (Hayes, 

1961, p. 15). Tolman and Robertson (1969) divided the 

felsites into two major groups-the Middlebrook 

Group and the younger Van East Group. Both groups 

are dominantly composed of rhyolite, although the 

Middlebrook Group has a higher potash-to-soda ratio 

than the Van East Group, which appears to be a more 

typical rhyolite (Hayes, 1961). Pratt (1978) noted the 

probable identification of a latitic assemblage in the 

lower part of the volcanic pile. Stratigraphic 

nomenclature of the volcanic rocks continues to evolve 

(Berry, 1976), but the system used in this study is that 

of Tolman and Robertson (1969). 

The intrusive granitic rocks, which range in texture 

from fine grained and slightly porphyritic to coarse 

grained, are divided into two groups which are believed 

to represent two distinct ·stages of emplacement. 

Rocks of the earlier stage, designated the Musco 

Group, are generally fine grained or porphyritic. Rocks 

of the later stage, designated the Bevos Group, consist 

of fine- to coarse-grained granite (Tolman and Robertson, 1969, p. 32). 

The Paleozoic rocks in the study area and adjoining 

parts of nearby States are included in four of Sloss' 

(1963) cratonwide lithic sequences. In ascending order, 

they are the Sauk, Tippecanoe, Kaskaskia, and 

Absaroka. These sequences are bounded by unconformities of continental proportions, each representing 

an important interval of geologic time. The Sauk 

strata are nearly pure dolomite in composition and are 

of Late Cambrian to Early Ordovician age. The overlying Tippecanoe sequence is composed largely of 

limestone and ranges in age from Middle Ordovician to 

Early Devonian. Strata in the Kaskaskia and Absaroka sequences contrast with the underlying Sauk 

and Tippecanoe in that shale generally forms a more 

prominent part of the local section. Also, sandstones in 

the Kaskaskia and Absaroka tend to be much less 

quartzose and carbonates tend to be much more 

argillaceous. These petrologic features reflect a fundamental change in depositional style during the midPaleozoic and, in the Illinois Basin at least, a change in 

location of source material as well (Potter and Pryor, 

1961). Kaskaskia strata range in age from Middle 

Devonian to Late Mississippian and the Absaroka in 

the study area is of Pennsylvanian age. 

Rocks of the Sauk sequence in the study area consist 

of a relatively thin, basal sandstone (the Lamotte 

Sandstone), the initial deposit of a transgressive sea, 

overlain by a thick sequence of dolomitized carbonates. 

Minor amounts of interbedded shale and siltstone occur in the lower part of the sequence (Elvins Group), 

and minor amounts of interbedded sandstone are scattered throughout the upper part of the sequence 

(Roubidoux through Powell Formations). These sandstones represent the regressive phase of late Sauk 

deposition (Sloss, 1963, p. 97) and are most prominent 

in tlie Roubidoux Formation. In central Missouri, the 

Roubidoux Formation is predominantly a quartzose 

sandstone whereas, in other parts of the State, as little 

as 10 percent of the formation contains sandstone and 

most of the rock is cherty dolomite, generally indistinguishable from dolomite in underlying formations (Koenig, 1961, p. 22). The sandstone is composed 

predominantly of fine- to medium-grained quartz sand. 

As a general rule, dolomites in the upper part of the sequence, consisting mostly of the Jefferson City Formation, tend to be fine grained and thin bedded, whereas 

dolomites in the lower part tend to be more coarsely 

crystalline and thicker bedded. Chert is locally abundant in the dolomites and, in the St. Francois Mountains area, large deposits of lead, zinc, and copper 

sulfide occur in rocks of the lower Sauk, mostly in the 

Bonneterre Formation (Kisvarsanyi, 1977, p. 436; 

Vineyard, 1977, p. 337). 

The Tippecanoe sequence in Missouri is relatively 

thin and contains numerous local unconformities. The 

St. Peter Sandstone or sandstone of the Everton Formation, representing the initial transgressive phase of 

Tippecanoe deposition, occurs at the base of the 

sequence. Most of the overlying formations are composed of clean, thin- to medium-bedded, fine- to 

medium-grained limestones or cherty limestones that 

in part have been dolomitized. Beds of shale (Decorah 

and Maquoketa Formations) occur in the middle of the 

sequence, and thin, interbedded sandstones occur 
30' 

15' 

-l 

I 

BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES 

45' 

I 

i 

ol 

U• 

zl 

01 t;l 

i!O• 

~I <• 

i3:1 

30' 

i .28 

I 

1 

' .. L!}<?~ ~--

1 

~~ I EXPLANATION 

,-J D Extrusive rocks 

I ·_ ": .. ;,·!Intrusive rocks 

~ REYNOLDS CO ! ------ -------L-1 Sampling locality in extrusive rocks 

i .19 Sampling locality in intrusive rocks 

10 15 20 25 KILOMETERS 

MISSOURI 

' , _ _1 _______ _ 

i 

FIGURE 3.-Generalized distribution of igneous rocks of Precambrian age in southeastern Missouri and distribution of sampling 

localities (modified from Tolman and Robertson, 1969). 

F5 
F6 GEOCHEMICAL SURVEY OF MISSOURI 

locally. Outcrops of Tippecanoe strata are restricted to 

the southeastern and eastern borders of the study area. 

Widespread uplift at the end of Early Devonian time, 

followed by extensive erosion, resulted in removal of 

many of the younger beds of the Tippecanoe sequence. 

Kaskaskia strata are extensively exposed in the 

northeastern, central, and southwestern parts of 

Missouri; in northeastern Oklahoma; and in northern 

Arkansas. The sequence is composed predominantly of 

cherty, coarse-grained, irregularly bedded limestone; 

but it also contains fine-grained limestone, tan 

dolomite, calcareous shale, and sandstone. Coarsegrained limestone, typified by the Burlington and 

Keokuk Limestones, is especially characteristic of the 

middle part of the section (upper Kinderhookian 

through lower Meramecian) in Missouri. Chert is 

widespread in these strata, particularly in Missouri, 

and generally occurs as discrete nodules, or layers interbedded with the carbonate layers. Shale is a minor 

component of the sequence in Missouri but forms a 

prominent part of the sequence in northeastern 

Oklahoma and northern Arkansas. In Missouri and 

Oklahoma this shale is generally silty and calcareous, 

and in northern Arkansas it is locally carbonaceous. 

Lower Absaroka (Pennsylvanian) strata crop out 

throughout most of northern and western Missouri, 

southern Iowa, eastern Kansas, southeastern 

Nebraska, northeastern Oklahoma, and northern 

Arkansas; these strata consist of cyclic deposits of interstratified shale, limestone, and sandstone. Shale is 

the dominant rock type, although limestone is a prominent component in northwestern Missouri and eastern 

Kansas, and sandstone forms an important part of the 

sequence in northeastern Oklahoma and northern 

Arkansas. The limestone tends to be argillaceous and 

the sandstone contains varying amounts of feldspar, 

rock fragments, mica, and iron-stained clay matrix. 

Extensive beds of bituminous coal occur in the lower 

part of the section, principally in the Des Moinesian 

Series. All in all, strata of Pennsylvanian age are the 

most geochemically diverse of those examined in the 

study. 

Numerous formations are recognized in the Pennsylvanian rocks. (See Koenig, 1961, p. 78-122; Merriam, 1963, p. 103-135.) The basal rocks (of Morrowan 

and Atokan age) are limited in outcrop to northern 

Arkansas, southeastern Oklahoma, and extreme 

southwestern Missouri. The overlying rocks (of Des 

Moinesian, Missourian, and Virgilian age) crop out in 

continuous bands over northern and western Missouri, 

eastern Kansas, and northeastern Oklahoma. Remnant 

outliers of DesMoinesian strata crop out on the north 

flank of the Ozark Uplift and contain economically important deposits of clay. Rocks of DesMoinesian age 

are several times as thick in southeastern Oklahoma 

(Arkoma Basin) as in Kansas and Missouri (platform 

area). The basin facies is predominantly shale with 

massive sandstone tongues, whereas the platform 

strata consist of cyclic deposits of sandstone, coal, 

limestone, and shale. The Arkoma Basin was quiet 

during Missourian and Virgilian time, and rocks of 

these ages are fairly uniform in thickness throughout 

the study area (Branson, 1962). These strata consist 

predominantly of shale and sandstone in the basin area 

and shale and limestone in the platform area. 

SAMPLING DESIGN 

Geochemical variability in this study was examined 

largely through the use of hierarchical sampling plans 

designed to estimate the proportions of the total geochemical variance at selected ranges of geographic 

scale within various bedrock geologic units (Miesch, 

1976). Such designs are essentially exploratory and are 

based on a system of hierarchically arranged sampling 

units such that each level of the hierarchy includes 

paired sampling units separated by a given distance or 

a selected range of distances. 

The general statistical model used in all phases of 

the geochemical survey of Missouri is as follows 

(Miesch, 1976): 

log X ijklmn=J.l+a ;+{3 ij+y ijk +d ijkt+'liJklm +E.ijklmn ( 1) 

For the bedrock units, X;Jklmn represents an analytical 

value reported on a rock sample by the laboratory: J.l 

represents the grand average (in logs) for all units 

studied; and the subscripted terms are deviations, each 

reflecting a separate source of variation, most of which 

are geographic in nature. The first of these terms, a;, 

represents the difference between J.l and the average (in 

logs) for the ith bedrock unit; the second, {3iJ, 

represents the difference between the average (in logs) 

of the jth area of the ith unit and the average for the ith 

unit; the third, YiJk• represents in most units the difference between the average (in logs) for the kth 

stratigraphic section in the jth area and the average of 

the jth area; the fourth, d;Jkt, represents in most units 

the difference between the average (in logs) for the lth 

portion of the kth section and the average of the kth 

section; and the fifth, 'liJktm, represents the difference 

between the logarithmic concentration of the mth sample in the lth stratigraphic portion and the average of 

the lth portion. The last term, E.;Jklmn, represents the difference between the logarithm of the reported concentration and the true logarithmic concentration. 

Logarithms of concentration in trace-element work are 

commonly employed to help meet some of the assump-
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F7 

tions underlying the statistical procedures used in 

data analysis (Miesch, 1976, p. 27). 

The model in equation 1 is a specific case of the 

analysis of variance (the hierarchical or "nested" case), 

and was first applied to a problem in field geology by 

Potter and Olsen (1954). It is discussed in mathematical detail in the context of a geochemical field problem 

by Krumbein and Slack (1956). Based on equation 1, 

the total observed logarithmic variance, S 2

1og x, is 

viewed as the sum of six estimated components, one 

for each subscripted term on the right side of 1: 

The variance components are, respectively, estimates 

of the variance among geologic units (S2 a), variance at 

large scales over each unit (S2p), variance between 

stratigraphic sections (S2

v), variance within stratigraphic sections (S2 6), variance between samples at a 

sampling site (S2 "), and analytical variance (S2 c). 

The model in equation 1 was modified for use in this 

study in order to overcome problems peculiar to 

sampling bedrock in the study area. Compositional 

variation among the bedrock units (S2 a) was not formally estimated because the geochemical disparity 

among the calcareous, aluminous, and siliceous units 

was expected to be obvious. Rather, each bedrock unit 

was examined using an independent sampling plan 

designed to estimate S2 p, S2 

y, and so forth. In all, 11 different sampling plans were established for the bedrock 

units, 4 of them in carbonate rocks (Sauk, Tippecanoe, 

and Kaskaskia carbonates, and carbonates of Pennsylvanian age); 4 in siliceous rocks (granitic rocks of 

Precambrian age, sandstones of the Roubidoux Formation, chert of the Kaskaskia sequence, and sandstones 

of Pennsylvanian age); 2 in shale (Kaskaskia shales 

and shales of Pennsylvanian age); and 1 in coal of 

Pennsylvanian age. A twelfth study was made of the 

lead-copper-zinc ores of the Southeast Missouri Lead 

Belt; and, throughout the study area, a few samples of 

minor intercalated, lithically distinct beds within the 

11 bedrock units were collected. No formal sampling 

designs were employed in collecting the ore samples or 

samples of these minor lithic units. 

Details of the sampling designs used are given 

below, and the 11 formal designs are summarized in 

table 1. In a general way, however, each component of 

variance defined in equation 2 reflects variation over a 

relatively specific range of geographic scales regardless of the bedrock unit studied. The second component, S2 p, reflects geographic variation at distances 

generally greater than 100 km, S2

v reflects variation at 

distances generally ranging from a few tens of 

kilometers to 100 or more kilometers (for the most part 

measured as differences between stratigraphic sections), S2 

6 reflects variation from a few tens of meters 

to many tens of kilometers (for the most part measured 

as differences within stratigraphic sections), and S2

" 

reflects variation among samples separated by as 

much as a few tens of meters in a sampling site. For 

most of the bedrock units, S2 6 was subdivided into two 

components, one (S29) reflecting stratigraphic variation 

over a few to many tens of kilometers and the other 

{S2 !C) representing stratigraphic variation from a 

few tens of meters to a few kilometers. The multiple 

sampling designs used in this study each constitute a 

stage 2a sampling scheme (Connor and others, 1972) in 

which each unit defined in the area of study is examined individually to determine the important scales 

of geochemical variation. 

The target population in this study is the aggregate 

of all potential bedrock samples of Precambrian and 

Paleozoic age in the study area. A sample is defined in 

geologically familiar terms as a few kilograms of rock 

cut or chipped from a homogeneous part (generally a 

single stratum) of bedrock. Because the only collecting 

tools used were geologic pick or sledge and chisel, the 

sampled population was confined to areas containing 

rock exposure, either natural or artificial. In order to 

minimize personal bias in estimation of the variance 

components, the samples were collected at randomly 

selected locations in outcrop. Moreover, in order to 

minimize analytical bias, all samples (and analytical 

splits) were submitted to the laboratory in a randomized sequence. The selection of areas sampled and 

stratigraphic sections depended on the outcrop 

distributions, but was considered effectively random 

because the outcrop distributions are controlled by a 

large number of complicated factors. 

PRECAMBRIAN ROCKS 

The distribution of sampling localities for the 

granitic and rhyolitic rocks of Precambrian age is 

shown in figure 3; specific locations and formations 

sampled are listed in table 2. Two randomly located 

samples were collected from surface exposures in each 

of 15 localities in each of the two general rock types: 

(1) granitic and associated intrusives, and (2) felsitic 

and associated extrusives. Each locality was about 

1 km2 in area, and each was located randomly in the 

area of outcrop. A total of 60 samples was collected. 

The two rock types are intermixed in outcrop, 

although the intrusive rocks are more prominent in the 

northern part of the St. Francois Mountains, and the 

extrusive rocks are more prominent in the southern 

part. Distances between sampling localities range from 

1 to 50 km. 
F8 GEOCHEMICAL SURVEY OF MISSOURI 

TABLE !.-Distribution of terms in the hierarchical statistical models used in sampling major bedrock units in Missouri and adjacent States 

[Greek letters are subscripts indicating hierarchical levels; nd, terms not defined] 

System or sequence and material sampled y 

Precambrian Sys tern: 

Granite and rhyolite-------------------- nd------ Major rock types 

Sauk sequence: 

Do 1 omi te-------------------------------- Areas of Strati graphic 

outcrop. sections within areas. Roubidoux Fonnation, sandstone only----- ---do--- -------do-------

Tippecanoe sequence: 

Subdivisions of bedrock units {a) 

Localities within outcrop nd---------------------------- Samples within areas of types. localities. 

Deciles of stratigraphic Percentiles of stratigraphic Samples within 

thickness within thickness within deciles. percentiles. 

sections. 

nd----------------------- nd---------------------------- Samp 1 es within 

sections. 

Limestone and dolomite------------------ nd------ Stratigraphic nd----------------------- Deciles of stratigraphic Samples within 

sections in area thickness within sections. deciles. 

of outcrop. 

Kaskaskia sequence: 

Limestone and dolomite------------------ Areas of Stratigraphic nd----------------------- ------------do---------------- Do. 

outcrop. sections within areas. S ha 1 e----------------------------------- ---do--- --------do-------- nd- ---------------------- nd- --------------------------- Samp 1 es within 

sections. 

Chert----------------------------------- ---do--- --------do-------- nd----------------------- nd---------------------------- Do. 

Pennsylvanian System: 

Shale----------------------------------- ---do--- --------do-------- Deciles of stratigraphic Percentiles of stratigraphic Samples within 

thickness within thickness within deciles. percentiles. 

sections. 

Sands tone------------------------------- ---do--- --------do-------- ---------do-------------- --------------do-------------- Do. 

Limestone and dolomite------------------ ---do--- --------do-------- ---------do-------------- --------------do-------------- Do. 

Coa 1------------------------------------ nd------ Mi nab 1 e beds------ nd----------------------- nd---------------------------- Samples within 

beds. 

TABLE 2.-Sampling localities of rocks of Precambrian age in 

Missouri 

Lac. rJo. Field No. 

(fig. 3) REIPC6 

7 

8 

9 

10 

11 

12 

13 

14 

15 

16 

17 

18 

19 

20 

21 

22 

23 

24 

25 

26 

27 

28 

29 

30 

01, 02 

03, 04 05, 06 

07. 08 09, 10 

11, 12 

13, 14 

15. 16 

17. 18 

19. 20 

21, 22 

23, 24 25, 26 

27. 28 29, 30 

31,32 

33, 34 

35, 36 37. 38 

39, 40 

41' 42 43, 44 45, 46 

47. 48 

49, 50 

51, 52 53, 54 

55, 56 

57. 58 

59, 60 

County North West 

1 at itude 1 ong i tude Stratigraphic Unit 1 

Iron--------- 37°17'35" 90°38'05" Mudlick Dellenite. 

Madison------ 37°26'15" 90°22'55" Felsite. 

-----do------ 37°24'55" 90°19'45" Do. 

-----do------ 37°31' 20" 90°24' 30" Middlebrook Group. 

-----do------ 37°29'35" 90°20'10" Felsite. 

-----do------ 37°32'40" 90°25'05" Middlebrook Group. 

Iron--------- 37°32'20" 90°35'20" Stouts Creek Rhyolite. 

-----do------ 37°31' 05" 90°36' 30" Do. 

-----do------ 37°32'35" 90°41'00" Royal Gorge Rhyolite. 

Reynolds----- 37°32'30" 90°48'55" Hogan Mountain Rhyolite. 

St. Francois- 37°46'45" 90°32'15" Stouts Creek Rhvol ite. 

-----do------ 37°44'30" 90°34'40" Hogan Mountain Rhyolite. 

-----do------ 37°40'30" 90°38'05" Middlebrook Group. 

Iron--------- 37°39 '40" 90°39' 1 0" Do. 

Washington--- 37°44'50" 90°54'35" Felsite. 

Madison------ 37°31 '50" 90°21 '05" 51 abtown Granite. 

-----do------ 37°34 '35" 90°09' 55" Granite. 

-----do------ 37°38'30" 90°21 '45" Slabtown Granite. 

-----do------ 37°36'45" 90°25'20" Butler Hill Granite. 

-----do------ 37°35' 45" 90°25 '20" Do. 

-----do------ 37°37 '00" 90°27' 00" Do. 

-----do------ 37°33' 40" 90°29 '25" Si 1 vermi ne Granite. 

-----do------ 37°34 '45" 90°30' 20" Do. 

Iron--------- 37°33'50" 90°33'05" Brown Mountain Rhyolite 

Porphyry. 

Reynolds 37°31 '35" 90°49'35" Munger Granite Porphyry. 

St. Francois- 37°41 '10" 90°30'45" Breadtray Granite. 

-----do------ 37°42' 20" 90°28 '45" But! er Hill Granite. 

-----do------ 37°49' 55" 90°37 '20" Granite. 

Washington--- 37°44 '35" 90°39' 25" Buford Granite Porphyry. 

Iron--------- 37°43 '40" 90°40' 05" Do. 

1

Modified from Tolman and Robertson, 1969. 

The components of geochemical variance estimated 

for the Precambrian rocks are: 

(3) 

These components reflect variation between the two 

rock types (S2 y), variation among sampling localities 

within rock types (S2e), variation between samples 

within localities (S2 "), and analytical variance (S2 E). 

SAUK SEQUENCE 

The distribution of sampling localities used in the 

study of the Sauk sequence is shown in figure 4; 

specific locations and formations sampled are listed in 

table 3. The sampling plan for the Sauk is based on six 

composite stratigraphic sections radiating outward 

from the St. Francois Mountains. These six sections 

were paired so that each pair represents an area of the 

total Sauk outcrop. The sections within each pair lie 

some 40-80 km apart. 

In the sampling plan for the carbonates (the dominant lithic type in the Sauk), each stratigraphic section 

was subdivided into 10 approximately equal parts 
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F9 

Precambrian rocks 

Sampling locality 

--Composite stratigr11phic 

v,.,.,,r-.,-../ section-Paired strati -

graphic sections 

"-""' " . .__,,'-/""'"· indicated 

~-------~ 

~~~~·~- I--

0 100 200 KilOMETERS 

FIGURE 4.-Sampling localities in the Sauk sequence. 

(deciles) from which 2 were randomly selected for 

sampling. Each of these 2 deciles was further subdivided into 10 approximately equal parts (percentiles), 

and 2 of the percentiles were selected randomly. From 

~ch percentile two samples of carbonate rock were collected at random, except at locality 7 (fig. 4), where 

only one sample was taken. Thus, a total of 4 7 carbonate samples was collected from this sequence. A 

stratigraphic decile iri these rocks encompasses about 

30 m of section in most of the State and as much as 

60 m of section on the edge of the Illinois Basin in 

southeasternmost Missouri. For the most part, the 2 

percentiles in each stratigraphic decile generally could 

be sampled in a single outcrop of carbonate. 

Based on this plan, six components of geochemical 

variance were estimated for the carbonate rocks of the 

Sauk: 

These components reflect variation among areas of 

outcrop (S2 p, where each area is represented by a pair of 

sampled sections), variation between stratigraphic sections within areas (S2 y), variation between strati-
FlO GEOCHEMICAL SURVEY OF MISSOURI 

TABLE 3.-Sampling localities of stratified bedrock units in Missouri and adjacent States 

Loc. No. 

(figs. 4, Field No. 

(REO-) 

State County North West Stratigraphic 

6' 7' 8) Unit 

2 

3 

4 

5 

6 

7 

8 

9 

10 

11 

12 

13 

14 

3 

15 

16 

4 

16 

17 

18 

19 

20 

21 

8 

22 

23 

latitude longitude 

Carbonate rocks of the Sauk sequence 

SDOl, SD02--------------Missouri--Iron-------------37°38 115"--91°02 100" 

SD03, SD04-----------------do----------do----------37°38 115"--91°02 100" 

S005, S006, S007, S008-----do-----Crawford---------37°50 150"--91°25 14511 

S009, SDlO-----------------do-----Washington-------37°45 155"--90°46 110" 

SOil, SD12-----------------do----------do----------37°45 155"--90°47 115" 

SD13, SD14-----------------do-----Franklin---------38°27 130"--91°00 125" 

SD15, SD16-----------------do----------do----------38°29 100"--9l 000 130" 

S017, SD18-----------------do-----Shannon----------37°08 145"--9l 026 140" 

SD19, SD20-----------------do----------do----------37°08 140"--9i 026 100" 

SD2l, SD22-----------------do-----Ozark------------36°35 105"--92°l7 155" 

SD23, SD24-----------------do----------do----------36°35 105"--92°l8 1l5" 

SD25-----------------------do-----Ripley-----------36°37 120"--90°50 100" 

SD27, SD28-----------------do----------do----------36°37 130"--90°49 150" 

SD29, S030, S031, SD32--Arkansas--Ra ndo 1 p h---------36°24 1 55"--90°55 115" 

SD33, S034--------------Missouri--Bollinger--------37°l7 140"--90°l3 100" 

SD35, SD36-----------------do----------do----------37°l5 110"--90°l2 115" 

SD37, SD38-----------------do-----Cape Girardeau---37°14 1 00"--89°48 115" 

SD39, SD40-----------------do----------do----------37°2l 140"--89°48 130" 

SD41, SD42-----------------do-----Ste Genevieve----37°47 120"--90°10 110" 

SD43, SD44-----------------do----------do----------37°47 120"--90°l0 120" 

SD45, SD46, SD47, SD48-----do----------do----------3]047 130"--90°04 100" 

Sandstone of the Sauk sequence 

SSOl, SS02--------------Missouri--Phelps-----------37°56 125"--9l 048 130" 

SS03, SS04-----------------do-----Washington-------37°45 155"--90°45 110" 

SS05, SS06-----------------do----------do----------38°08 100"--9l 000 130" 

SS07, SS08-----------------do-----Franklin----------38°36 100"--9l 003 100" 

SS09-----------------------do----------do-----------38°27 130"--9l 0U0 125" 

SSlO-----------------------do-----Warren------------38°37 100"--91°01 130" 

SSll, SS12-----------------do-----Texas-------------37°03 135"--9l 039 155" 

SS13-----------------------do-----Ozark-------------36°36 140"--92°25 105" 

SS14-----------------------do----------do-----------36°35 110"--92°33 140" 

SS15, SS16-----------------do-----Carter------------3r00 140"--90°59 155" 

SS17-----------------------do-----Ripley------------36°40 100"--90°52 120" 

SS18-----------------------do----------do-----------36°37 120"--90°50 100" 

SS19, SS20--------------Arkansas--Rando 1 ph----------3o 024 1 55"--90° 55 1 00" 

SS2l, SS22--------------Missouri--Madison-----------37°34 120"--90°23 110" 

SS23, SS24-----------------do-----Bollinger---------37°l8 150"--90°00 105" 

Bonneterre Formation. 

Potosi Dolomite. 

Eminence Dolomite. 

Bonneterre Formation. 

Do. 

Jefferson City Formation. 

Do. 

Gasconade Dolomite. 

Do. 

Roubidoux Formation. 

Jefferson City Formation. 

Roubidoux Formation. 

Jefferson City Formation. 

Cotter Formation. 

Gasconade Dolomite. 

Do. 

Jefferson City Formation. 

Do. 

Bonneterre Formation. 

Do. 

Gasconade Dolomite. 

Roubidoux Formation. 

Lamotte Sandstone. 

Gunter Sandstone Member 

of Gasconade Dolomite. 

Roubidoux Formation. 

Jefferson City Formation. 

Jefferson City Formation. 

Roubidoux Formation. 

Jefferson City Formation. 

Do. 

Gunter Sandstone Member 

of Gasconade Dolomite. 

Roubidoux Formation. 

Do. 

Cotter Formation. 

Lamotte Sandstone. 

Roubidoux Formation. 

24 SS25-----------------------do-----Ste Genevieve-----37°48 100"--90°15 155" Lamotte Sandstone. 

SS26-----------------------do----------do-----------37°47 140"--90°l6 105" Do. 

13 SS27, SS28-----------------do----------do-----------37°47 140"--90°03 150" Roubidoux Formation. 

Shale of the Sauk sequence 

25 SHOl, SH02--------------Missouri--Washington--------37°46 145"--90°53 140" Davis Formation. 

13 SH05, SH06-----------------do-----St Genevieve------37°47 100"--90°08 130" Do. 

Carbonate rocks of the Tippecanoe sequence 

26 TLOl, TL02--------------Missouri--Cape Gi rardea u---37 °15 145"--89°35 1 00" Jose him Do 1 amite. 

27 TL03, TL04-----------------do----------do----------37°l8 100"--89°3l 100" Kimmswick Limestone. 
Loc. No. 

(figs. 4 

6, 7' 8,) 

28 

29 

BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES 

TABLE 3.-Sampling localities of stratified bedrock units in Missouri and adjacent States-Continued 

Field No. 

(REO-) 

State County North West 

latitude longitude 

Carbonate rocks of the Tippecanoe sequence--Continued 

TL05, TL06-----------------do-----Jefferson--------38°l5 115"--90°24•oo" 

TL07, TL08-----------------do----------do----------38°l7 100"--90°23 130" 

TL09, TLlO-----------------do-----Ralls------------39°31 135"--91°21 100" 

TLll, TL12-----------------do----------do----------39°3l 145"--91°2l•oo" 

Sandstone of the Tippecanoe sequence 

Strati graphic 

Unit 

Joachim Dolomite. 

Plattin Limestone. 

Decorah Formation. 

Kimmswick Limestone. 

26 TSOl, TS02--------------Missouri--Cape Girardeau----37°15 130"--89°38 130" StPeter Sandstone. 

28 TS03, TS04-----------------do-----Jefferson---------38°l4 130"--90°23 130" Do. 

Shale of the Tippeanoe sequence 

28 THOl, TH02--------------Missouri--Jefferson---------38°l5.15"--90°24 100" Joschim Dolomite. 

TH04-----------------------do----------do-----------38°l6 156"--90°23 115" Decorah Formation. 

30 TH03-----------------------do-----Pike--------------39°27 145"--9l 024 145" Maquokata Formation. 

Carbonate rocks of the Kaskaskia sequence 

31 MLOl, ML02--------------Missouri--St Charles--------38°49 150"--90°44 155" Keokuk Limestone. 

ML03, ML04-----------------do-------------do--------38°48 120"--90°44 125" Warsaw Formation. 

30 ML05, ML06, ML07, ML08-----do-----Pike--------------39°24 100"--9l 02l 155" Burlington Limestone. 

32 ML09, Mll 0, Mlll, ML12-----do-----Boone-------------38°55 1 35"--92°17 140" Do. 

33 ML13, ML14-----------------do-----Pettis------------38°49 105"--93°l3 135" Sedalia Limestone. 

ML15, ML16-----------------do-------------do--------38°49 105"--93°l3 135" Burlington Limestone. 

34 ML17, ML18-----------------do-----Hickory-----------37°49 105"--93°35 100" Northview Shale Sedalia 

Limestone. 

ML19,ML20------------------do-------------do--------37°49 120"--93°32 155" Burlington Limestone. 

35 ML21, ML22-----------------do-----Lawrence----------37°09 100"--93°42 110" Compton Limestone. 

36 ML23, ML24-----------------do-------------do--------37°05 120"--93°51.40" Keokuk Limestone. 

37 ML25, ML26--------------0klahoma--Mayes-------------36°26 1l5"--95°03 130" Reeds Spring Member of 

Boone Formation. 

38 ML27, ML28----------------do--------------do--------36°ll•oo"--95°l5•oo" Fayetteville Shale. 

39 ML29, MUO----------------do------Sequoyah----------35°36 100"--94°52 100" Hindsville Limestone. 

ML31, ML32----------------do--------------do--------35°36 100"--94°52 100" Fayetteville Shale. 

40 ML33, ML34--------------Arkansas--Searcy------------35°58 130"--92°53.00" Boone Formation. 

ML35, ML36----------------do--------------do--------35°59 120"--92°53.40" Do. 

41 ML37, ML38----------------do------Stone-------------35°56 100"--92°07 130" Fayetteville Shale. 

ML39, ML40----------------do--------------do--------35°56 100"--92°07 130" Pitkin Limestone. 

Sandstone of the Kaskaskia sequence 

45 FLOl, FL02--------------Mi ssouri--Buc hanan----------39°48 • 20"--94°41 1 15" I a ton Limes tone. 

46 FL03, FL04-----------------do-----Andrew------------39°54 130"--94°53 130" Plattsmouth Limestone 

Member of Dread Limestone. 

FL05, FL06-----------------do-------------do--------39°54 145"--94°53 110" Lecompton Limestone. 

FLO?, FL08-----------------do-------------do--------39°55 120"--94°54 145" Ozawkie Limestone Member 

of Deek Creek Limestone. 

47 FL09, FLlO-----------------do-----Johnson-----------38°33 145"--93°35 135" Verdigris Limestone Member 

of Senora Formation. 

48 FL 11, FL12-----------------do-----Cass--------------38°30; 45"--94 °06 145" Marma ton Group 

Fll 

49 FL13--------------------Kansas----Douglas-----------39ooo•oo"--95°22 150" Rock Bluff Limestone Member 

of Deer Creek Limestone. 

FL14-----------------------do-------------do--------39ooo•oo"--95°22 150" Ervine Creek Limestone Member 

of Deer Creek Limestone. 

50 FL15, FL16-----------------do-----Shawnee-----------39°02 105"--95°36 105" Curzon Limestone Member of 

Topeka Limestone. 
F12 GEOCHEMICAL SURVEY OF MISSOURI 

TABLE 3.-Sampling localities of stratified bedrock units in Missouri and adjacent States-Continued 

Loc. No. 

(figs. 4 

6, 7, 8} 

Field No. 

(REO-) 

State County North West 

latitude longitude 

Strati graphic 

Unit 

51 FL17, 

52 FL19, 

53 FL2l, 

FL23, 

54 FL25, 

55 FL27, 

56 FL29, 

57 FL31, 

58 PHOl, 

PH03, 

59 PH05, 

60 PH09, 

PHll, 

61 PH13, 

62 PH15, 

63 PH17, 

PH19, 

53 PH21, 

PH23, 

64 PH25, 

65 PH27, 

66 PH29, 

PH31, 

Sandstone of the Kaskaskia sequence--Continued 

FL 18--------------Oklahoma- -Nowa ta------------36°44' 00 11 --95°48' 0011 Hogs hooter Limestone. 

FL20-----------------do-----Washington--------36°43'4011 --95°57'3011 Dewey Limestone. 

FL22-----------------do-----Osage-------------36°40'l5 11 --96°24'45 11 Deer Creek Limestone. 

FL24-----------------do-------------do--------36°40'l511 --96°24'4511 Topeka Limestone. 

FL26-----------------do-----Tulsa-------------36°05'25 11 --95°47'15 11 Senora Formation. 

FL28-----------------do-------------do--------35°54'4011 --95°47'5511 Fort Scott Limestone. 

FL30-----------------do-----L i nc.ol n-----------35°45 • 00 11 --96°40 '1 011 Reading Limes tone Member 

of Emporia Limestone. 

FL32-----------------do-------------do--------35°43'50 11 --96°44'00 11 Brownville Limestone Member 

of Wood Siding Formation. 

Shale of Pennsylvanian age 

PH02--------------Missouri--Daviess-----------39°~5'25 11--93°S7'35 11 Kansas City Group. 

PH04-----------------do-------------do--------39°55'20 11 --93°57'5011 Do. 

PH06, PH07, PHOS--Kansas----Jackson-----------39°35'4511 --95°36'3511 Wabaunsee Group. 

PHlO--------------Missouri--Cass--------------38°38'15 11 --94°21'15 11 Pleasanton Formation. 

PH12-----------------do-------------do--------38°40'3011 --94°22'3511 Do. 

PH14-----------------do-----Clay--------------39°ll'4011 --94°35'2011 Wyandotte Limestone. 

PH16--------------Kansas----Wyandotte---------39°05'2511 --94°53'5511 Vilas Shale. 

PH18--------------0klahoma--Osage-------------36°46'0011 --96°04'4511 Barnsdall. 

PH20-----------------do-------------do--------36°44'5011 --96°08'2511 Tallant Formation. 

PH22-----------------do-------------do--------36°40'l5 11 --96°24'45 11 Calhoun Shale. 

PH24-----------------do-------------do--------36°40'3011 --96°25'0011 Severy Shale. 

PH26-----------------do-----Tulsa-------------35°58'25 11 --95°55'3011 Nowata Shale. 

PH28-----------------do-------------do--------36°04'4511 --95°53'1011 Holdenville Shale. 

PH30-----------------do-----Creek-------------3S0 59'20 11 --96°ll'0011 Nellie Bly Formation. 

PH32-----------------do-------------do--------35°55'2511 --96°l4'5011 Do. 

Chert of Kaskaskia sequence 

31 MCOl--------------------Missouri--St. Charles-------38°49'50 11 --90°44'55 11 Keokuk Limestone. 

MC02----------------------do--------------do--------38°48'2011 --90°44'3011 Do. 

30 MC03, MC04----------------do------Pike--------------39°24'0011 --9l 02l'5511 Burlington Limestone. 

32 MC05, MC06----------------do------Boone-------------3B055'3511 --92°l7'4011 Do. 

33 MCO?----------------------do------Pettis------------38°49'05 11 --93°13'0511 Sedalia Limestone. 

MCOS----------------------do--------------do--------38°49'0511 --93°13'0511 Burlington Limestone. 

34 MC09----------------------do------Hickory-----------37°49'05 11 --93°35'00 11 Northview Shale Sedalia 

Limestone. 

MClO----------------------do--------------do--------37°49'20 11 --93°32'5511 Burlington Limestone. 

35 MCll----------------------do------Lawrence----------37°09'0011 --93°42'1011 Reeds Spring Member of 

Boone Formation. 

36 MC12----------------------do--------------do--------3J005'20 11 --93°5l'4011 Keokuk Limestone. 

37 MC13--------------------0klahoma--Meyes-------------36°26'l511 --95°03'3011 Reeds Spring Member of 

Boone Formation. 

38 MC14----------------------do--------------do--------36°ll'00 11 --95°l5'0011 Keokuk Limestone 

39 MC15, MC16----------------do------Sequoya h----------35°36' 0011 --94°52' 0011 Boone Formation 

40 MCl?--------------------Arkansas--Searcy------------35°58'30 11 --92°53'00 11 Do. 

MClS----------------------do--------------do--------35°59'2011 --92°53'4011 Do. 

41 MC19, MC20----------------do------Stone-------------36°55'3011 --92°06'45 11 Do. 
Loc. No. 

(figs. 4, 

6, 7' 8) 

67 

68 

69 

62 

49 

70 

71 

72 

53 

73 

74 

BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES 

TABLE 3.-Sampling localities of stratified bedrock units in Missouri and adjacent States-Continued 

PSOl, 

PS03, 

PS05, 

PS07, 

PS09, 

PSll, 

PS13, 

PS17, 

PS19, 

PS21, 

PS23, 

PS25, 

Fie 1 d No. 

(REO-) 

State County North West 

latitude longitude 

Sandstone of Pennsylvanian age 

Stratigraphic 

Unit 

PS02--------------Missouri--Carroll-----------39°34'05"--93°l6'45" Cabaniss Group. 

PS04-----------------do-------------do--------39°35'15"--93°l8'10" Do. 

PS06-----------------do-----Livingston--------39°45'00"--93°40'00" Pleasanton Formation. 

PS08-----------------do-------------do--------39°55'35"--93°57'00" Do. 

PSlO--------------Kansas----Wyandotte---------39°05'30"--94°53'40" Lansing Group. 

PS12-----------------do-----Douglas-----------38°59'55"--95°l8'40" Lawrence Formation. 

PS14-----------------do-----Wabaunsee---------39°03'30"--96°0l'OO" Wabaunsee Group. 

PS18--------------0klahoma--Craig-------------36°40'30"--95°20'00" Senora Formation. 

PS20-----------------do-----Nowata------------36°42'00"--95°29'30" Labette Shale. 

PS22-----------------do-----Osage-------------36°4l'00"--96°27'30" Silver Lake Shale Member 

of Seraton Shale. 

PS24-----------------do-------------do--------36°4l'l5"--96°32'30" Wabaunsee Group. 

PS26-----------------do-----Wagoner-----------35°57'05"--95°34'30" Blue jacket Sandstone 

Fl3 

Member of Boggy Formation. 

PS27, 

66 PS29, 

PS31, 

75 COl, 

C03, 

76 C05, 

77 COl, 

78 C09, 

Cll, 

79 Cl3, 

80 Cl5, 

81 Cl7, 

82 Cl9, 

83 C21, 

C23, 

84 C25, 

85 C27, 

C29, 

PS28-----------------do-------------do--------35°57'05"--3~ 37'40" Oolagah Limestone. 

PS30-----------------do-----Creek-------------35°59'30"--96°09'20" Nellie Bly Formation. 

PS32-----------------do-------------do--------35°59'20"--96°ll'OO" Do. 

Coal of Pennsylvanian age 

C02----------------Missouri--Barton------------37°22'00"--94°35'30" Rowe Coal. 

C04-------------------do-------------do-----.:.--37°22'00"--94°35'30" Drywood (Kniveton) Coal. 

C06-------------------do-----Vernon------------37°42'25"--94°28'30" Mineral Coal. 

C08-------------------do-------------do--------38°0l'20"--94°22'00" Do. 

ClO-------------------do-----Henry-------------38°18'00"--94°00'00" Weir-Pittsburg Coal. 

Cl2-------------------do-------------do--------38°18'00"--94°00'00" Tebo Coal. 

Cl4-------------------do-------------do--------38°2l'00"--93°52'45" Do. 

Cl6-------------------do-------------do--------38°26'30"--93°42'15" Do. 

Cl8-------------------do-----Putnam------------40°32'30"--92°50'45" Lexington Coal. 

C20-------------------do-----Macon-------------39°45'15"--92°43'30" Mulky Coal. 

C22-------------------do-------------do--------39°39'30"--92°30'15" Bevier Coal. 

C24-------------------do-------------do--------39°39'30"--92°30'15" Mulky Coal. 

C26-------------------do-----Randolph----------39°33'45"--92°37'15" Bevier Coal. 

C28-------------------do-----Boone-------------39°03'00"--92°14'00" Do. 

C30-------------------do-------------do--------39°05'30"--92°l8'15" Summit Coal. 

Shale of Kaskaskia sequence 

31 MHOl--------------------Missouri--St. Charles-------38°48'20"--90°44'30" Warsaw Formation. 

30 MH03, MH04-----------------do-----Pike--------------39°27'30"--9l 024'30" Hannibal Shale. 

33 MHOS, MH06-----------------do-----Pettis------------38°47'50"--93°l3'30" Chouteau Limestone. 

34 MHO?, MH08-----------------do-----Hickory-----------37°49'05"--93°35'00" Northview Shale. 

35 MH09, MHlO-----------------do-----Lawrence----------37°09'00"--93°42'10" Do. 

42 MHll, MH12--------------0klahoma--Delaware----------36°23'15"--94°56'00" Chattanooga Shale. 

38 MH13, MH14-----------------do-----Mayes-------------36°ll'l5"--95°l4'30" Fayetteville Shale. 

39 MH15, MH16-----------------do-----Sequoya h----------35°3 7'15"--94 °49' 00" Chattanooga Sha 1 e. 

MH17, MH18-----------------do-------------do--------35°35'00"--94°52'00" Fayetteville Shale. 

43 MH19, MH20--------------Arkansas--Searcy------------35°54'00 --92°37'00" Fayetteville Shale. 

41 MH21-----------------------do-----Stone-------------35°52'45"--92°06'15" Ruddell Shale Member of 

Moorefield Formation. 

MH22-----------------------do-------------do--------35°52'40"--92°06'10" Do. 
F14 GEOCHEMICAL SURVEY OF MISSOURI 

graphic deciles within sections (S2

9), variation between 

percentiles within deciles (S2)(), variation between 

samples within percentiles (S2 "), and analytical 

variance (S2 £). 

A suite of samples was collected of the sulfide ore 

that occurs in the lower Sauk strata in the Southeast 

Missouri Lead Belt. Twenty-seven samples of ore and 

concentrate, collected over a mill-operating period of at 

least 10 days, were obtained from seven mining and 

milling operations (fig. 5). 

TIPPECANOE SEQUENCE 

In addition to the carbonate samples, 28 samples of 

sandstone and four samples of shale were also collected 

from the Sauk sections. Twelve of the sandstone 

samples were collected from the Roubidoux Formation 

(fig. 4, table 3), two from each of the same sections used 

in the study of the carbonates. These 12 samples were 

used to estimate four components of geochemical 

variance: 

(5) 

These components reflect variation among the 

three areas of outcrop (S2p), variation between 

stratigraphic sections within the areas (S2 y), variation 

between samples within the sections (S2 "), and 

analytical variance (S2 £). 

The distribution of sampling localities used in the 

study of the Tippecanoe sequence is shown in figure 6; 

specific locations and formations sampled are listed in 

table 3. Samples of carbonate rocks were collected 

from three composite stratigraphic sections-one each 

in the southeastern, central, and northeastern parts of 

the outcrop area of eastern Missouri. Each section was 

subdivided into 10 approximately equal parts (deciles), 

and two randomly located samples were collected from 

each of two randomly selected deciles, for a total of 12 

samples. A stratigraphic decile in these rocks encompasses about 4.5 m of section in the northeastern part 

GASCONADE 1 FRANKLIN 1 r---j-----~--------1._, JEFFERSON 

I I ~ I I ' /-./ I 1 e2 D~;----~ I O<AWFORD I WASHING10N I ST FRANCOIS/ I I I / 

I I I % ./, 

_L __ .... I Ll ~ :; I <~" ""' / 

T

-e3 --~-~-----j <9~ """ I 

L__ c I '1.)- '/'J 

5 ~OC< L / 

STE GENEVIEVE 

MISSOURI 

PERRY 

Area of 

figure 5 

DENT • ~ _T _______ L 

~---~-~--;--~-~ I i ---~-~~/1.-'-

.....__, 1 moN I MADISON 1 1 

SHANNON 

-----~ •

4 

REYNOlDS ! i I BOLL~GER ! 

I 7 I I I I ~· I ~-----TJ I 

I ~---.J WAYNE I 

0 25 50 KILOMETERS 

CAPE 

GIRARDEAU 

FIGURE 5.-Maj<>r lead mining and milling operations in southeastern Missouri showing sampling localities (numbered dot). Mine-Mill 

operations: 1, Federal Division, St. Joe Minerals Co.; 2, Indian Creek Division, St. Joe Minerals Co.; 3, Viburnum Division, St. Joe 

Minerals Co.; 4, Fletcher Division, St. Joe Minerals Co.; 5, Magmont, Cominco American Inc.; 6, Buick, Missouri Lead Operating 

Co.; 7, Sweetwater, Ozark Lead Co. (Modified from Wharton and others,1969, p. 59.) 
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F15 

of the outcrop belt and about 12m in the southeastern 

part. 

The components of geochemical variance estimated 

for carbonate in the Tippecanoe are: 

(6) 

These components reflect variation among stratigraphic sections (S2 v), variation between stratigraphic 

deciles within sections (S2 x), variation between samples 

within deciles (S2 "),. and analytical variance (S2 £). Concurrent with the carbonate sampling, four samples 

each of intercalated sandstone and shale were also collected from the Tippecanoe (fig. 6, table 3). 

I 

I 

' I I 

I 

3]0 ·r----'------~- ·- I 

I 

---, 

0 50 

KASKASKIA SEQUENCE 

The distribution of sampling localities used for the 

Kaskaskia sequence are shown in figure 7; specific 

locations and formations sampled are listed in table 3. 

For the carbonates, five pairs of stratigraphic sections 

were sampled around the outcrop belt; thus, each pair 

represents an area of outcrop. The sections in each pair 

are spaced about 80 km apart. Each section was subdivided into 10 approximately equal stratigraphic 

parts (deciles), and two randomly selected samples 

were collected from each of 2 randomly selected 

deciles, for a total of 40 carbonate samples. A 

stratigraphic decile ranges from about 4.5 m of section 

·-· I 

-~ \ r1 \ I 

------... ---o..-----·1 I I I 

~-. 

I ·-----t-' I 

I EXPLANATION 

.----

1 

I I I 

,...._.:_ ' _____ ..l...~r----1 I I 

I I 

~ I 

Tippecanoe sequence 

@ I 

Sampling locality 

100 KILOMETERS 

FIGURE G.-Sampling localities in the Tippecanoe sequence. 
F16 GEOCHEMICAL SURVEY OF MISSOURI 

--r------.. ' I I • • I I • • I I I ;_ ____ i 

--·----T-! 

38': i 

i 

i 

i 

I I 

EXPLANATION 

I Kaskaskia sequence '--------' 

Sampling localityPaired stratipraphic 

sections ind1cated 

. .-· 35~,';;"r----'---'----L.~·~O~KI..A~HO~M~A~~:!:.J=-:.::·-:_:-~T~! ,, 96" 95' __ __!_____l:::2~=.J~~~~;c=-:.:.':"'J. __ ~f;::~L:bL_~~__{-__!__!"4f!.~r-;_ _ __L~ 100 200KILOMETERS 

'---~----~-----~' 

FIGURE 7.-Sampling localities in the Kaskaskia sequence. 

in west-central Missouri to about 26 m in northern 

Arkansas. 

The components of geochemical variance estimated 

for the carbonate rocks of the Kaskaskia sequence are: 

(7) 

These components reflect variation among the five 

areas of outcrop (S2

11), variation between stratigraphic 

sections within areas (S2 y), variation between 

stratigraphic deciles within sections (S2 x), variation between samples within deciles (S2 ,.), and analytical 

variance (S2 c). 

Because both shale and chert form locally prominent 

parts of the Kaskaskia sequence, the geochemical 

variation in each was examined using the same 

stratigraphic sections as those used in the study of the 

carbonate rocks. A single sample of chert was collected 

from each decile sampled in the carbonate study, 

resulting in 20 samples (fig. 7, table 3). For shale (ex-
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F17 

eluding the organic-rich Chattanooga Shale at the base 

of the Kaskaskia), two randomly selected samples were 

taken from 8 of the 10 sections used in the carbonate 

study, and 1 sample was collected from a ninth section 

(locality 31) for a total of 17 shale samples (fig. 7, table 

3). The components of geochemical variance for chert 

and shale in the Tippecanoe are the same as those 

estimated for sandstone in the Roubidoux Formation. 

(See equation 5.) 

All but the basal few formations of the Kaskaskia in 

the study area are of Mississippian age, and the carbonate and chert samples collected from these strata 

are exclusively Mississippian in age. However, four 

samples of Chattanooga Shale of Devonian age (basal 

Kaskaskian) in northeastern Oklahoma and two of the 

Devonian Sylamore Sandstone in southeastern 

Missouti were collected. ·Finally, two samples of sandstone were collected from the Bushberg Sandstone 

(Mississippian) in southeastern Missouri (fig. 7, 

table 3). 

PENNSYLVANIAN SYSTEM 

The distribution of sampling localities used in the 

study of the Pennsylvanian System is shown in figure 

8; specific locations and formations sampled are listed 

in table 3. Samples of shale, sandstone, and carbonate 

were collected from four composite stratigraphic sections, two located in the northern part of the outcrop 

belt, and two in the southern part. The sections in each 

pair are separated by about 80 km. Each section was 

subdivided into 10 approximately equal stratigraphic 

parts (deciles), and 2 deciles were selected randomly. 

Each selected decile was subdivided into 10 approximately equal stratigraphic parts (percentiles), and two 

randomly selected samples were taken from each of 2 

randomly selected percentiles, making a total of 32 

samples of each lithic tye, except for sandstone for 

which the two required samples could not be located in 

one of the percentiles. 

A decile in these rocks encompasses about 45 m of 

section in the northern pair of sections and about· 

110 min the southern pair. The 2 percentiles in each 

selected decile could generally be sampled in a single 

outcrop, but the deciles in each section were located as 

much as 120 km apart. The components of geochemical 

variance estimated for the shale, sandstone, and carbonate of Pennsylvanian age are the same as those 

estimated for carbonate rocks in the Sauk sequence. 

(See equation 4.) 

Independent of the shale, sandstone, and carbonate 

studies, 15 coal beds, ranging in thickness from 30 to 

107 em, were sampled from the working face in 11 

operating strip pits in Missouri (fig. 8, table 3). The 

total thickness of each bed was subdivided into 8-cm 

sectior..s, two of these sections were selected randomly, 

and a composite sample was collected in each, for a 

total of 30 coal samples. The components of 

geochemical variance estimated for coal are: 

(8) 

These components reflect variation among coal beds 

(S2 v), variation between samples within coal beds (S2 "), 

and analytical variance (S2 £). 

ANALYTICAL METHODS AND 

DATA EVALUATION 

The rocks collected during the course of this study 

were analyzed by a variety of laboratory methods 

(table 4). Much of the trace element analysis is based 

on a semiquantitative emission spectrographic technique. This technique was supplemented by methods 

based on X -ray fluorescence, atomic absorption, and 

specialized techniques for determining fluorine and 

arsenic concentrations. Details of the analytical procedures are described in Miesch (1976, p. 10-17). All 

analyses were made in laboratories of the U.S. 

Geological Survey. 

All rock samples were collected from outcrop and 

trimmed of obvious weathering rinds or other surface 

features. The lead-zinc-copper ore samples consisted of 

mined or milled material. Coal samples were collected 

from working faces at strip mines. Each sample was 

crushed in a jaw crusher and ground in a ceramic mill 

to minus-100-mesh particle size. Before grinding, randomly selected samples of each lithic type were divided 

into two parts using a Jones splitter, thus permitting 

an estimate of analytical variance (table 5). 

The coal samples were not washed or subjected to 

flotation techniques, but were ground to pass through 

a 100-mesh sieve. A part of the ground material was 

weighed, then burned to ash in a muffle furnace in 

which the heat was increased 50 o C each half hour to a 

temperature of 525 o C and held at this temperature for 

about 24 hours. The resulting ash was then weighed to 

determine the ash yield of the coal. Analytical methods 

for most elements employed a weighed aliquot of the 

ash and are the same as those previously described for 

rock materials. For determining concentrations of 

arsenic, fluorine, mercury, and selenium, all of which 

may be volatilized and lost by burning the sample, 

weighed aliquots of raw coal were used for analysis. 

The methods of analysis used for these elements were, 

respectively, spectrophotometric, specific-ion electrode, flameless atomic absorption, and X-ray 

fluorescence. 
F18 GEOCHEMICAL SURVEY OF MISSOURI 

I I 

EXPLANATION 

~ Post-Pennsylvanian rocks 

8 Pennsylvanian rocks-Showing ., 

top of Des Moinesian Series (-D-) 

~ Pre-Pennsylvanian rocks 

@ Sampling locality 

@l Coal pit sampling locality 

--- Paired composite stratigraphic section I ~-1 

359.';::" 1 

! 

--'---'---L11,i/O~KLA~HO~M~A~~:!:._J::_-:_:--:_:-~.,..;1-J 96~ 95' __ _i___j::2~=.J~~~~J;:~'J_ __ J::;p::::.::::L_bL__lJ;;;--J _ _;__~~y,--____;~---'-~g'.5" 

100 200KILOMETEAS 

FIGURE B.-Sampling localities in the Pennsylvanian System. 

Elements determined on coal ash were converted to 

concentrations in the raw coal prior to data evaluation 

using the relation: 

C=AP/(100) (9) 

where C estimates the concentration in raw coal, A is 

the concentration observed in ash, and Pis the percent 

ash. 

Because of the unusually high concentrations of copper and zinc in the lead-zinc-copper sulfide ores, these 

two elements were determined in ore by an atomic absorption method. 

Insofar as possible, all samples of each lithic type 

were analyzed in a randomized sequence, thus converting any potential analytical drift into a random 

variation which cannot be mistakenly construed as 

geological in origin. Each sample was analyzed for 55 
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F19 

TABLE 4.-Analytical methods, with·approximate lower limits of determination, for elements in this study 

Element Analytical method 

Lower Limit 

of determination (parts 

per mill ion) 

Element 

Lower limit 

Analytical method of determinnation (parts 

per million) 

Ag----------- Spectrographic-------------

Al----------- X-ray fluorescence---------

As----------- Colorimetric---------------

8------------ Spectrogrphic-------------- Ba----------- -----------do--------------

Be----------- -----~-----do--------------

C, carbonate- Gasometric-----------------

C, organic--- Calculated-----------------

Ca----------- X-ray fluorescence---------

Cd----------- ----------do---------------

Ce----------- Spectrographic-------------

Co----------- ----------do---------------

Cr----------- ----------do---------------

Cu----------- ----------do---------------

F------------ F selective ion electrode--

Fe----------- X-ray fluorescence---------

Ga----------- Spectrographic-------------

Ge----------- ----------do---------------

Hg----------- Flameless atomic absorption 

In----------- Spectrographic-------------

K------------ X-ray fluorescence---------

La----------- Spectrographic-------------

0.5 

l 0,000 

l 

20 

1.5 

l 

500 

1,000 

1,000 

l 

150 

2 

l 

l 

10 

1,000 

5 

10 

.01 

10 

1,000 

30 

elements. Depending on the sample composition, 15 

additional elements, most of them rare earths, were on 

occasion looked for; and both organic carbon and inorganic (carbonate) carbon concentrations were determined. About 34 elements were consistently detected 

in most shale, coal, granite, and sulfide ore samples, 

and about 23 were routinely detected in most sandstone and carbonate samples. The analytical data on 

which this report is based are too voluminous for inclusion here, with the exception of data on the lead-zinccopper ores. All other chemical data have been published in Boerngen, VanTrump, and Ebens (1975). 

The frequency distributions of trace element determinations commonly exhibit a marked positive 

skewness, that is, low concentrations tend to be much 

more frequently observed than high concentrations. 

As a consequence, the average value in such a distribution will substantially overestimate the most common, 

or expected, value (the mode); and the standard deviation may give rise to an unrealistic range in probable 

concentration. In order to circumvent such difficulties, 

summary statistics of most of the distributions in this 

study are based on logarithms of the data. The 

geometric mean (GM), defined as the antilog of the 

average of the logarithmic concentrations, is generally 

Li---------- Atomic absorption--

Mg---------- ---------do--------

Mn---------- Spectrographic-----

Me---------- ---------do--------

Na---------- Atomic Absorption 

Nb---------- Spectrographic 

Nd---------- ---------do--------

Ni---------- ---------do--------

P----------- X-ray fluorescencePb---------- Spectrographic-----

Sb---------- ---------do--------

Se---------- ---------do--------

Se---------- X-ray fluorescenceSi---------- -----------do------

Sn---------- Specteographic-----

Sr---------- ---------do--------

Ti---------- ---------do-------- V----------- ---------do-------- Y----------- ---------do--------

Yb---------- ---------do--------

Zn---------- Atomic absorption--

Zr---------- Spectrographic 

5 

300 

l 

3 

100 

10 

70 

5 

300 

10 

150 

5 

. l 

10,000 

10 

5 

2 

7 

10 

l 

10 

10 

a less biased estimate of the median. The geometric 

deviation (GD), defined as the antilog of the standard 

deviation of the logarithmic concentrations, is a factor 

useful in computing probable expected ranges in concentration. For example, if a distribution is lognormal, 

about 68 percent of the determinations in a randomly 

selected suite should fall within the limits GM/GD and 

GMXGD. About 95 percent should fall within the 

range GM/(GD) 2 to GMX(GD)2

, and over 99 percent 

should be within the range GM/(GD)3 to GMX(GD)3

• 

Commonly a suite of samples may contain one or 

more elements in concentrations too low to be 

measured by the analytical method used. In these circumstances the element distribution is said to be censored, and a problem arises as to how to estimate the 

mean and variance (or their logarithmic counterparts) 

in an unbiased manner. Miesch (1967, 1976) described 

procedures based on a method of Cohen (1959) that 

constitute an adjustment of the mean and variance 

computed for the uncensored part of the data. The 

same adjustment can be made if censoring occurs at 

the higher end of the distribution. 

Many kinds of statistical analyses, however, require 

completely uncensored data, and the following arbitrary practice was used to circumvent problems of 
F20 GEOCHEMICAL SURVEY OF MISSOURI 

TABLE 5.-Estimated variance of the analytical procedures (including sample preparations) for five rock types sampled in 

Missouri and adjacent States 

[The variance estimates are based on duplicate analyses of 10 samples of granitic rocks; 15 

samples of carbonate rocks; 15 samples of sandstone and chert; 15 samples of clay and 

silt;'and 15 samples of coal. Leaders H indicate no data available] 

Analytical loglO variance (S~) Element or Sands tone C1 ays tone, silts tone, ash Granitic rocks Carbonate rocks and chert and shale Coal 

Al----------- 0.0003 0.0074 0.0031 0. 0005 0.0074 

tAs----------- .0026 .0102 .0438 .0067 .0623 

Ash---------- .0103 

8------------ .0215 .0562 .0099 Ba----------- .0008 .0128 .0088 .0099 .0365 

Be----------- .0062 1

.o7o5 

.0104 .0046 c, carbonate- .0922 .0223 

c. organic--- .1418 .0815 .0544 

Ca----------- .0001 1.2333 .0150 .0005 .0261 Co----------- .0107 .0102 .0130 

Cr----------- .0123 .0155 .0049 .0122 Cu----------- .0052 .0130 .0083 .0082 .0191 F------------ .2931 .0449 .0164 .1284 .0091 Fe----------- .0001 .0003 .0039 .0001 .0228 Ga----------- .0309 .0005 .0032 

Ge---------- .0069 Hg---------- .0281 .0164 .0171 .0250 .0288 

K----------- <.0001 .0022 (.0001 .0001 .0099 La---------- .0054 .0034 .0059 l i---------- .01.05 .0002 .0184 

Mg---------- .0010 .0008 .0349 .0074 .0092 Mg( dolomite) 1

.2030 

Mn---------- .0078 .0124 .1238 .0051 .0133 Mo---------- .0071 Na---------- .0001 .0242 .0260 .0350 .0060 

Nb---------- .0039 .0099 Nd---------- .0045 Ni---------- .0014 .0248 .0072 .0180 P----------- .0359 .0941 .0277 .0187 Pb---------- .0315 .0170 .0075 .0158 .0173 

Sc---------- .0115 <.0001 .0069 .0170 Se---------- .0573 .0848 .0498 .0569 .0304 Si---------- 1 2. 7ooo .0008 ~.2333 .0001 .0091 Sr---------- .0040 .0082 .0094 .0049 .0110 Ti---------- .0018 .0193 .0121 .0048 .0103 

V----------- .0073 .0007 .0032 .0069 Y----------- .0036 .0016 .0007 .0059 .0081 Yb---------- .0052 .0021 .0033 .0140 Zn---------- .0003 .0560 .0032 .0012 .0869 Zr---------- .0201 .0036 .0148 .0268 .0213 

1Variance calculated on nontransformed data. 

censoring when necessary. If less than a third of the 

frequency distribution of any element in any unit of 

study was censored, a value equal to approximately 

seven-tenths of the lower limit of determination was 

used in place of the censored values. The only justification for such a replacement is that substitution of any 

reasonable value below the analytical limit would not 

substantially alter geochemical conclusions drawn 

from the statistical analysis. 

Finally, the problem arises as to whether the area 

means (most areas being represented by a pair of 

sampled stratigraphic sections) are sufficiently different to form the basis of a geochemical map. If not 

sufficiently different, any resulting map may be 

unstable, that is, not generally reproducible on repetition of the field sampling and laboratory analysis. Too 

few areas were sampled within each geologic unit in 

this study to warrant the construction of maps, but it 

still seems useful to identify those situations where the 

area means were sufficiently different to meet the 

criteria for geochemical mapping. Where these criteria 

are met, the means and associated statistics for the 

areas are given separately on the tables summarizing 

the geochemical data. 

A basic criterion for the sufficiency of differences 

among means is the conventional F-statistic which is 

based on measures of variance between and within 

areas. If the· F-statistic is found to be statistically 

significant, one can have a prescribed confidence that, 

at the least, one of the areas is different from some 

other. However, this does not seem to be an adequate 

criterion for predicting whether the general configuration of a geochemical map would be reproducible. 

Several more stringent empirical criteria were described by Miesch (1976, p. A9-A10). The one used 

here requires that the variance of the area means, E8 , 

be smaller than a critical value, Er. Er is the maximum 

permissible variance for an area mean if the F-statistic, 

given by: 

(10) 

(11) 

and using only 1 and 2nr-2 degrees of freedom, is 

significant at the 0.05 probability level. The term nr is 

the minimum number of randomly collected samples 

needed from each area (if random sampling were 

employed) and can be read from a graph in Miesch 

(1976, p. A9). 

In situations where all hierarchical sampling levels 

(listed in table 1) were used, Es is computed by: 

and Er is computed by: 

(13) 

The subscripted n's in equation 12 are the number of 

sampling units at each level of the hierarchical design. 

Where E s is larger thanE n the number of samples collected within each area (based on the hierarchy) is effectively less than the critical number nn required by 

the variance ratio, v (equation 11). 
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F21 

GEOCHEMICAL VARIABILITY 

LIMESTONE AND DOLOMITE 

Limestone and dolomite are the most widespread 

rocks in the near-surface landscape of the study area. 

They compose most of the Sauk, Tippecanoe, and Kaskaskia strata, underlying much of eastern and 

southern Missouri and northern Arkansas (fig. 3); and 

they are scattered as tabular lenses through the Pennsylvanian strata in northwestern Missouri and eastern 

Kansas (fig. 3), where they tend to support broad interfluves. Carbonate aquifers are the main source of 

drinking water supplies in southern Missouri and 

northern Arkansas. 

The carbonate rocks are also important because of 

the large deposits of lead, zinc, and copper sulfide ore 

contained in them in the southeastern and southwestern parts of Missouri. In addition, limestone and 

dolomite are two of the major mineral commodities 

produced in the State. Major uses are as crushed and 

broken stone for concrete aggregate, roadstone, cement, lime manufacture, riprap, and agriculture. 

Throughout much of the southern part of the study 

area, prolonged weathering of these rocks has resulted 

in a cherty, clay-rich, base-deficient soil of poor 

agricultural quality. 

Normative mineral compositions of 131 samples of 

carbonate rock are compared in figure 9. In computation of these norms, all MgO was put into dolomite, 

and excess CaO into calcite. The normative clay component was assumed to contain 26 percent Al20a and 

50 percent Si02, proportions which approximate those 

found in illitic mica (Weaver and Pollard, 1973, p. 9). 

Excess Si02 was computed as quartz, which occurs in 

these rocks as both sand and chert. Over half of the 

samples consist of more than 90 percent normative 

calcite and dolomite combined. Few contain more than 

20 percent normative quartz and clay combined, and 

all but two of those are of Mississippian and Pennsylvanian age. 

The distribution in figure 9 shows the following: 

(1) The Sauk carbonates consist of reasonably pure 

dolomite (sample SD09 from the Bonneterre Formation being the only exception), and carbonate in the 

lower Sauk (pre-Jefferson City strata) tends to be 

slightly purer dolomite than that in the upper Sauk. 

(2) The Tippecanoe carbonates consist largely of 

Quartz + "clay" 

5 X X XffX X 

o xg 

50 ML26 50 

5 0 • 

0 0 

0 

0 

• 

8 

Calcite L."-----------,;-----

1

----7

0 

Dolomite Pl3lx Calcite t10----"'-r>----"-'----'-'----""'----/~Dolomite 

"'- 5 ML17o / "- o ML38 o ML16 / 

"- PUS x Pl22 Pl3Qx PL32 / 

"'- o 

6 ML04A / 

' X ~ / ' . / """' / xPL23 0 • 

"- x& o PL08xoML20 oSD09 6T~1 • / 

Calcitl'...___,.,__ _____ ---"'-!..:==-,...------------.... /oolomite 

50 

FIGURE 9.-Normative mineralogy of limestone and dolomite samples of the lower Sauk sequence (circle), the upper Sauk sequence (dot), the Tippecanoe sequence (triangle), the Kaskaskia sequence (square), and of Pennsylvanian age (X). Numbered 

samples are referred to in text. 
F22 GEOCHEMICAL SURVEY OF MISSOURI 

relatively pure limestone, although three samples 

(TL01, TL05, and TL06, all from the Joachim Formation) are normative dolomites. (3) Carbonate of the 

Kaskaskia sequence contains both limestone and dolomite. Nine of forty samples consist of reasonably pure 

dolomite (two of these are fairly siliceous-ML16 and 

ML17), and a tenth (ML20) is distinctly dolomitic. 

These 10 samples were collected in Missouri, and 9 of 

them (all except ML04) are Early Mississippian in age 

(Kinderhookian or Osagean). Two of the limestones 

(ML26 and ML36) are distinctly siliceous. (4) Carbonate of Pennsylvanian age is largely limestone, some 

of it siliceous (PL22 and PL25) or dolomitic (PL08 and 

PL23). Four dolomite samples (PL29, PL30, PL31, and 

PL32), collected from the Brownville Limestone 

Member of the Wood Siding Formation and the 

Reading Limestone Member of the Emporia 

Limestone at the top of the Pennsylvanian section in 

Oklahoma (loc. Nos. 56 and 57, fig. 8), represent a 

localized carbonate variant. They were taken from redcolored, fine-grained, thin, poorly bedded strata which 

contrast strongly with the more ordinary gray, thinly 

bedded, fossiliferous limestones of Pennsylvanian age 

in Kansas and Missouri. 

Results of the analysis of variance for these four carbonate units are given in tables 6-9, and summary 

statistics are given in tables 10-13. Carbonate rocks in 

the Sauk appear to be distinctly more uniform 

geochemically than carbonate rocks in the three other 

intervals studied. The total observed variation (S2

1og x, 

table 6) of all elements except carbonate carbon, 

calcium, magnesium, and titanium is nearly as small as 

or smaller in the Sauk than that estimated for the 

other three carbonate units (figs. 7-9). Moreover, the 

total observed variance in barium, fluorine, iron, 

silicon, and titanium tends to be smaller in both the 

Sauk and the Pennsylvanian carbonates (figs. 6, 9) 

than in carbonates of the Tippecanoe and Kaskaskia 

(figs. 7, 8). Thus, the less widespread carbonate units 

appear to be more geochemically variable than the 

more widespread units. 

The between-areas variance (S2 p, between pairs of 

sections) is generally small in the carbonate rocks of 

this study, except for those of Pennsylvanian age 

(table 9). The Pennsylvanian rocks are the only ones to 

consistently exhibit elemental variation between areas 

of more than 10-15 percent of the total estimated 

variance. This variability is statistically significant for 

four elements (chromium, potassium, phosphorus, and 

titanium) and reflects in part the higher concentrations 

found in the samples from Oklahoma. Copper in the 

Sauk (table 6) is the only other element in the carbonate rocks showing statistically significant variation at this scale. Five carbonate samples collected at 

loc. Nos. 2, 3, and 4 (fig. 4) are unusually high in copper 

(7-20 ppm) when compared to an expected level of 2 

ppm (table 10). All of these samples were collected in or 

near the Washington County Barite District, an area 

of known anomalous near-surface copper. Although no 

visible indications of mineralization were noted at the 

points of collection, the rocks cropping out in the 

sampled areas may be weakly mineralized. 

Area averages for copper in the Sauk and chromium, 

potassium, phosphorus, and titanium in the Pennsylvanian were examined for stability as described 

above. E s was computed by: 

Es= S2v + S2e + S2x: +82"+S2c 

2 4 8 16 (14) 

The pertinent parameters for this examination are 

listed below: 

Element v nr Er Es 

Sauk sequence 

Copper ....................... 0.49 8 0.0110 0.0131 

Pennsylvanian carbonates 

Chromium .................... .32 11 .0070 .0064 

Potassium .................... .30 12 .0103 .0109 

Phosphorus .................. .59 7 .0289 .0154 

Titanium ..................... .21 16 .0129 .0176 

Area averages for only chromium and phosphorus in 

Pennsylvanian carbonate are sufficiently stable 

(Es~r) to be listed in the summary statistics (table 

13). Additional data are required if stable averages for 

the remaining three elements are to be computed. 

Between-section variance (S2 y) is most prominent in 

the carbonates of the Kaskaskia sequence. Nine 

elements in this unit, including magnesium, exhibit 

statistically significant variation between sections 

within areas of outcrop. The presence of magnesium in 

this element group suggests that this variation reflects 
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F23 

TABLE 6.-Components of variance estimated for carbonate rocks of the Sauk sequence 

[Variance calculated on data transformed to logarithms, except as noted. Asterisk(*), value significantly greater than zero at the 0.05 probability level] 

Total Between areas Between sections Element 1 oglO 

variance 

2 Percent Percent 

(Slog X) Component of Component of 

(S2) total ($2) total 

f3 y 

Ba---------- 0.2856 0.0 <1 0.0453 16 

C, carbonate1 .6383 .0215 3 .1234 19 

Ca 1--------- 3.7063 .1889 5 .1552 4 

Cr---------- .1745 0 <1 .0725 42 

Cu---------- .1315 *.0432 33 .0158 12 

F----------- .1921 0 <1 .0154 8 

Fe---------- .1446 0 <1 .0536 37 

Hg---------- .0922 0 <1 .0264 29 

K----------- .2722 0 <1 .1023 38 

Mg --------- 3.8368 0 <1 *1.2122 32 

Mn---------- .2389 0 <1 .0625 26 

Na---------- .0289 0 <1 .0041 14 

Se---------- .0824 0 <1 0 <1 

Si---------- .2304 .0193 8 .0148 6 

Sr---------- .0267 0 <1 0 <1 

Ti---------- .4754 0 <1 .0647 14 

1Variance calculated on nontransformed data. 

TABLE 7.-Components of variance estimated for carbonate rocks of 

the Tippecanoe sequence 

[Variance calculated on data transformed to logarithms, except as noted. Asterisk(*), value 

significantly greater than zero at the 0.05 probability level] 

Variance 

Total Between sections Between dec il es Between samples 

Element 1 og variance 

(5~og xl Percent Percent Percent 

Component of Component of Component of 

(52) total (5~) total (52 +52) total y n ( 

Ba---------- 0.4942 o.o <1 *0.4497 91 0.0444 9 

C, carbonate 1 1.3973 0 <1 * .9568 68 .4405 32 C, organic-- .1650 0 <1 *.1094 66 .0556 34 

Ca 1--------- 99.6371 0 <1 *82.0679 82 17.5992 18 

Cr---------- .1717 .0106 6 .0809 47 .0802 4 7 

F----------- .5798 0 <1 .2307 40 .3491 60 

Fe---------- .1986 0 <1 *.1315 66 .0671 34 Hg---------- .1676 0 <1 0 <1 .1676 100 

K----------- .2842 0 <1 *. 204 7 72 .0795 28 Mg---------- .4916 0 <1 *.4194 85 .0721 15 Mn---------- .1753 .0300 17 *.1161 66 .0293 17 

Na---------- .1343 0 <1 * .1203 90 .0140 10 5e---------- .0869 0 <1 .0480 55 .0389 45 5i---------- .4309 0 <1 * .3426 79 .0883 20 5r---------- .1268 0 <1 *.1 077 85 .0191 15 Ti---------- • 8735 0 <1 .5632 64 .3103 36 Zn---------- .0341 *.0137 40 .0106 31 .0098 29 

1 Variance ca1cu1 a ted on nontransformed data. 

Variance 

Between deciles Between percentiles Between samples 

Percent Percent Percent 

Component of Component of Component of 

($2) total (S2) total {$2 +$2) total 

8 K n £ 

*0. 1654 58 0.0 <1 0.0758 27 

*.1590 25 .1252 20 .2092 33 

0 <1 *1.6687 45 1.6935 46 

*.0574 33 .0027 2 .0418 24 

0 <1 .0102 8 .0622 47 

.0207 11 0 <1 .1553 81 

*.0545 38 .0101 7 .0265 18 

*.0222 24 .0030 3 .0406 44 

*.1148 42 .0044 2 .0508 19 

0 <1 .1287 3 2.4960 65 

*.0915 38 .0277 12 .0571 24 

*.0105 37 0 <1 .0142 49 

0 <1 .0131 16 .0693 84 

*.0732 32 0 <1 .1230 53 

*.0155 58 0 <1 .0112 42 

*.2588 54 .0028 1 .1491 31 

in part the uneven distribution of dolomite from section to section. Fluorine, iron, mercury, manganese, 

and sodium are distinctly higher in the dolomite than 

in the limestone samples from this sequence, whereas 

strontium is distinctly lower (table 12). Yttrium and 

zinc are slightly lower in the dolomite. Maximum yttrium levels of 50-70 ppm were detected in carbonate 

samples from loc. No. 32 (Missouri) and No. 40 (Arkansas). More than 100 ppm zinc were found in one sample 

from loc. No. 31 (fig. 7). In the other three carbonate 

units, only magnesium in the Sauk, zinc in the Tippecanoe, and silicon in the Pennsylvanian exhibit a 

statistically significant variance component at the 

between-section scale (S2v)· Variation in the 

magnesium and silicon reflects variation in proportions of dolomite and quartz (chert), respectively, from 

section to section. The variation in zinc reflects slightly elevated levels (as much as 22 ppm) in Tippecanoe 

samples from loc. No. 28 (fig. 6) . 

Stratigraphic variation (S2

9+S2

x) is large in all units. 

More than half of the elements listed in tables 6-9 ex-
F24 GEOCHEMICAL SURVEY OF MISSOURI 

TABLE B.-Components of variance estimated for carbonate rocks of the Kaskaskia 

sequence 

{Variance calculated on data transformed to logarithms, except as noted. Asterisk(*), value significantly 

greater than zero at the 0.05 probability level) 

Variance 

Total Between areas Between sections Be tween dec i 1 es Be tween s amp 1 es 

Element 1 oglO 

variance 

(S~og xl Percent Percent Percent Percent 

Component of Component of Component of Component of 

(S~) total (S~) total (s;) total (S~ +S;) total 

Ba---------- 0.6919 o.o <1 0.1960 28 *0.3700 53 0.1259 18 

C, carbonate I 2.8499 0 <1 0 <1 .6977 24 2.1522 76 

C, organic-- .1318 .0130 10 0 <1 .0058 4 .1129 86 

Ca 1--------- 112.4386 0 <1 38.9863 35 26.2827 23 47.1695 42 

Cr---------- .2641 0 <1 .0380 14 *.1625 62 .0636 24 

F----------- .6071 0 <1 * .3013 50 * .1387 23 .1671 27 

Fe---------- .3246 0 <1 *.1866 57 * .0987 30 .0393 12 

Hg---------- .1398 0 <1 * .0844 60 .0208 15 .0346 25 

Mg---------- .6030 0 <1 * .3628 60 *.2005 33 .0398 6 

Mn---------- .0972 .0375 39 *.0216 22 .0017 2 .0365 38 

Na---------- .1766 0 <1 * .1164 66 *.0252 14 .0350 20 

Se---------- .1282 0 <1 .0141 11 .0043 3 .1098 86 

Si---------- .4305 0 <1 0 <1 *.2620 61 .1684 39 

Sr---------- .3124 0 <1 * .2692 86 .0114 4 .0318 11 

Ti---------- 1.2834 0 <1 .3456 27 *. 7667 60 .1711 14 

Y----------- .0869 0 <1 * .0214 25 .0234 27 .0422 49 Zn---------- .0506 .0001 <1 *.0089 18 .0164 32 .0252 50 

1Variance calculated on nontransformed data. 

TABLE 9.-Components of variance estimated for carbonate rocks of Pennsylvanian age 

[Variance calculated on data transformed to logarithms, except as noted. Asterisk(*), value significantly greater than zero at the 0.05 probability level] 

Variance 

Total Between areas Between sections Between decil es Between percentiles Between samples 

Element 1 oglO 

variance 

(S2 X) Percent Percent Percent Percent Percent 

Log Component of Component of Component of Component of Component of 

(S2) total (52) total (S2) total (S2) total (S2 +S2) total 

B y e K n E 

As--------- 0.2214 0.0358 16 0.0118 5 *0.0636 29 o.o <1 0.1102 50 

Ba--------- .2294 .0116 5 .0248 11 0 <1 *. 1297 57 .0633 28 

C, carbonate 1 1.8762 .1 097 6 .4679 25 .0447 2 :3562 19 .8977 48 

Ca -------- 93.5272 10.3323 11 7.7837 8 *59.5987 64 0 <1 15.8125 17 

Cr--------- .1 025 *.0251 25 0 <1 0 <1 .0255 25 .0519 51 

Cu--------- .1089 .0016 1 0 <1 0 <1 *.0556 51 .0518 48 

F---------- .2906 0 <1 0 <1 .0359 12 .0607 21 .1940 67 

Fe--------- .1573 .0129 8 0 <1 .0732 47 *.0358 23 .0355 23 

Hg--------- .2224 0 <1 .0347 16 0 <1 *.0919 41 .0958 43 

K---------- .1613 *.0374 23 0 <1 .0062 4 .0313 19 .0864 54 

Mg--------- .3773 .0301 8 0 <1 *.2700 72 0 <1 .0772 20 

Mn--------- .1400 .0172 12 .0183 13 *.0440 31 .0158 11 .0446 32 

Na--------- .1485 .0035 2 0 <1 .0256 17 .0251 17 .0943 63 

P---------- .3220 * .1198 37 .0062 2 0 <1 0 <1 .1961 61 

Se--------- .1843 .0075 4 .0007 <1 0 <1 .0556 30 .1206 65 

Si--------- .2253 .0174 8 *.0685 30 0 <1 .0533 24 .0860 38 

Sr--------- .3437 0 <1 .1340 39 *.1582 46 .0095 3 .0420 12 

Ti--------- .2497 *.0430 17 0 <1 0 <1 .0757 30 .1309 52 

V---------- .1288 .0290 23 0 <1 *.0336 26 .0142 11 .0520 40 

Zn--------- .1340 .0395 30 0 <1 *.0441 33 .0053 4 .0450 34 

Zr--------- .1279 .0265 21 0 <1 .0432 34 *.0334 26 .0248 19 

1Variance calculated on nontransformed data. 
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F25 

TABLE 10.-Geochemical summary of rocks of the Sauk sequence in Missouri and adjacent States 

(GM, geometric mean, except as noted; GD, geometric deviation, except as noted; Ratio, number of samples m which element detected to total number of samples; ppm, parts per million; 

leaders (--1 indicate no data available] 

Dolomite Sandstone of the 

Roubidoux Formation 

Element 

GM GO Ratio GM GO Ratio 

Al, percent-- 0.31 2.18 16:47 0.43 1.75 6:12 

As, ppm------ 1 • 1 2. 51 27:47 1.1 1.57 7:12 

B, ppm------- <20 0:47 18 1.78 6:12 

Ba, ppm------ 8.8 3.42 47:47 38 1.92 12:12 

Be, ppm------ <1 0:47 <1 0:12 

C, carbonate, 

percent--- 112 2 .80 47:47 <.01 6:12 

C, organic, 

percent--- .11 3.04 27:47 .30 3.13 11:12 

Ca, percent-- 121 22.28 47:47 3.017 6:12 

Co, ppm------ <3 4:47 <3 1:12 

Cr, ppm------ 3.6 2.62 47:47 2.0 2.47 10:12 

Cu, ppm------ 2.0 2.30 39:47 1.2 2.14 8:12 

F, ppm------- 91 2.74 44:47 9.8 4 .• 83 6:12 

Fe, percent-- • 17 2.40 45:47 .090 3.26 7:12 

Ga, ppm------ <5 2:47 <5 0:12 

Hg, ppm------ .028 2.01 46:47 .0079 2.82 6:12 

K, percent--- .19 3.32 38:47 .083 2.99 7:12 

La, ppm------ <30 0:47 <30 0:12 

Li, ppm------ 1.1 2.66 5:47 2.1 2.47 3:12 

Mg, percent-- 111 2 2.52 47:47 3.22 12:12 

Mn, ppm------ 83 3.08 47:47 29 3.42 12:12 

Mo, ppm------ .81 2.97 7:47 <3 0:12 

Na, percent-- .027 1.48 47:47 .013 2.53 12:12 

Nb, ppm------ <10 0:47 <1 0 0:12 

Ni, ppm------ <5 2:47 <5 1:12 

P, ppm------- 94 2. 51 12:47 100 2.22 5:12 

Pb, ppm------ <10 7:47 <10 0:12 

Sc, ppm------ <5 0:47 <5 0:12 

Se, ppm------ .18 1.94 35:47 .086 2.06 6:12 

Si, ppm------ 1.5 3.02 39:47 140 2 8.06 12:12 

Sr, ppm------ 100 1.46 47:47 13 2.23 12:12 

Ti, ppm------ 33 4.89 46:47 83 5.63 12:12 

Y, ppm------- <10 0:47 <10 0:12 

Yb, ppm------ <1 0:47 <1 0:12 

v, ppm------- 6.4 2.04 28:47 5.3 1.43 5:12 

Zn, ppm------ 6.4 2.04 17:47 5.2 1. 61 2.12 

Zr, ppm------ 7.1 1.88 20:47 22 1.63 12:12 

1Arithmetic mean. 2Standard deviation. 3Median. 

hibit statistically significant variation at one or the 

other of these scales. Such variation is expected 

because compositional layering is a distinguishing 

feature of sedimentary rocks. The large-scale 

stratigraphic variation in the Sauk carbonates reflects 

mostly the slightly higher argillic content of the upper 

Sandstone (except Roubidoux) Shale of the Davis Formation 

GM GO Ratio Observed range Ratio 

0.67 2.55 8:14 7.9 - 9.0 4:4 

1.0 2.08 6:14 

20 2.11 7:14 100 - 150 4:4 

77 2.47 14:14 300 - 500 4:4 

<1 0:14 1 1. 5 4:4 

<.01 6:14 .21 - 1.5 4:4 

.31 1.43 14:14 • 1 - 2.7 4:4 

(.07 4:14 3.9 - 4.6 4:4 

<1 0 1:14 10 - 15 4:4 

2.8 2.84 13:14 100 - 150 4:4 

1.3 2.55 8:14 7 - 20 4:4 

26 6.41 9:14 

.11 3.38 9:14 2.0 - 3.4 4:4 

<5 4:14 30 4:4 

<.01 8:14 .02 - .07 4:4 

.32 5.43 11 :14 .83 - 9.1 4:4 

<30 0:14 50 4:4 

<5 7:14 16 - 20 4:4 

.085 7.73 14:14 1.3 - 2.8 4:4 

40 4.39 14:14 70 - 150 4:4 

>7 1:14 

.018 2.90 14:14 .052- .096 4:4 

<10 0:14 <10 0:4 

<7 1:14 20 - 30 4:4 

210 1.38 12:14 130 - 440 4:4 

<10 5:14 <10 - 15 2:4 

<5 0:14 15 4:4 

.13 1.69 10:14 <.1 - .4 3:4 

143 7.78 14:14 20 - 22 4:4 

14 2.36 14:14 200 - 300 4:4 

130 2.39 14:14 2000 -3000 4:4 

<10 2:14 10 - 15 4:4 

<1. 5 2:14 1 1. 5 4:4 

<7 5:14 70 - 100 4:4 

<11 3:14 15 - 43 4:4 

41 2.26 14:14 70 4:4 

Sauk (fig. 9) compared to the lower Sauk. In general, 

the upper Sauk has slightly less total carbonate and 

slightly more barium, chromium, iron, potassium, 

sodium, silicon, and titanium. The large-scale 

stratigraphic variation (S2e) in the carbonates of Pennsylvanian age reflects the presence of four dolomite 
F26 GEOCHEMICAL SURVEY OF MISSOURI 

TABLE H.-Geochemical summary of rocks of the Tippecanoe sequence in Missouri and adjacent States 

[GM, geometric mean, except as noted; GD, geometric deviation, except as noted; Ratio, number of samples in which element detected to total number of samples; ppm, parts per million; 

leaders(-) indicate no data available] 

Combined data for 

limestone and dolomite Limestone only Dolomite only Shale St. Peter Sandstone 

Element 

GM GO Ratio GM GO Ratio Observed Observed Observed 

range Ratio range Ratio range Ratio 

A1. percent-- <0.53 3:12 <0.53 1:9 <0.53 - 1.6 2:3 3.2 - 6.4 4:4 <0.53 0:4 

As, ppm------ .74 1. 53 3:12 1 0:9 1.0 - 1.5 3:3 3.4 - 7.8 4:4 <1 0:4 

8, ppm------- <20 1 :12 <20 0:9 <20 - 20 1 :3 30 - 100 4:4 <20 - 30 2:4 

Ba, ppm------ 5.6 5.04 10:12 3.0 3.75 7:9 20 - 70 3:3 150 - 700 4:4 10 - 20 4:4 

Be, ppm------ <1 0:12 <1 0:9 0:3 <1 2 2:4 <1 0:4 

C, carbonate, 

percent---- Ill 2 1.18 12:12 Ill 2 1.16 9:9 10 - 12 3:3 .59 - 5.8 4:4 <.01 - .03 2:4 

C, organic, 

percent---- .28 2.55 12:12 .28 2.50 9:9 .1 .6 3:3 <.1 .4 2:4 .1 .4 4:4 

Ca, percent-- 1

32 2 8.44 12:12 136 2 3.19 9:9 17 - 27 3:3 .71 - 9.3 4:4 <.071 0:4 

Co, ppm------ <3 1 :12 <3 0:9 <3 - 3 1 :3 5 - 10 4:4 <3 0:4 

Cr, ppm------ 2.7 2.60 11 :12 1.8 1.94 8:9 7 - 15 3:3 50 - 100 4:4 1 - 2 4:4 

Cu, ppm------ .84 3. 51 6:12 .60 1.99 3:9 3 - 5 3:3 15 - 20 4:4 <1 0:4 

F,ppm-------- 67 5.77 10:12 32 3.77 7:9 36 - 62 3:3 950 -3300 4:4 <10 - 70 3:4 

Fe, percent-- .ll 2.79 10:12 .074 1. 51 7:9 .28 - .56 3:3 1.2 - 3.4 4:4 <.070 0:4 

Ga, ppm------ <5 1 :12 <5 0:9 <5 - 7 1 :3 10 - 20 4:4 <5 0:4 

Hg, ppm------ .022 2.57 ll :12 .018 2.40 8:9 .02 - .07 3:3 .01 - .11 4:4 <.01 - .01 2:4 

K, Percent--- .12 3.41 8:12 .077 2.46 5:9 .5 - 1.4 3:3 3.0 - 5.9 4:4 <.083 0:4 

La, ppm------ <30 0:12 <30 0:9 0:3 <50 - 50 1:4 <30 0:4 

Li, ppm~----- 1.2 6.26 3:12 <5 0:9 9 - 18 3:3 33 - 90 4:4 <5 0:4 

Mg, percent-- 1.2 5.03 12:12 1.0 2.62 9:9 7.7 - 11 3:3 .98 - 5.5 4:4 .006- .018 4:4 

Mn, ppm------ llO 2.62 12:12 llO 2.82 9:9 70 -150 3:3 50 -2000 4:4 1.5 - 15 4:4 

Mo, ppm------ <5 0:12 <5 0:9 0:3 <5 5 1:4 <5 0:4 

Na, percent-- .013 2.33 12:12 .0093 1.41 9:9 .030- .037 3:3 .052- .089 4:4 <.007- .007 1:4 

Ni, ppm------ <5 0:9 <5 0:9 <5 

P, ppm------- <220 4:12 <220 3:9 <220 

Pb, ppm------ 4.0 2.06 2:12 <1 0 0:9 <10 

Sc, ppm------ <5 0:12 <5 0:9 

Se, ppm------ .16 1.97 9:12 .18 1.83 7:9 <.1 

Si, percent-- 1.0 4.53 9:12 <.47 6:9 1.9 

Sr, ppm------ 360 2.27 12:12 440 2.11 9:9 150 

Ti, ppm------ 350 10:12 3

50 7:9 70 

v. ppm------- 3.9 2.42 4:12 <7 1 :9 <7 

y' ppm----- <10 1 :12 <10 1 :9 

Yb, ppm---- <1 0:12 <1 0:9 

Zn, ppp---- 12 1.53 9:12 12 1.54 7:9 <10 

Zr, ppm---- <10 4:12 <10 1:9 10 

1Arithmetic mean. 2Standard deviation. 3Median. 

samples (loc. Nos. 56 and 57, fig. 8). Compared to the 

other Pennsylvanian carbonates (table 13), these 

samples are high in manganese and vanadium, as well 

as in magnesium, and are low in calcium and strontium. Variation in arsenic and zinc at this scale reflects 

the presence of three samples from loc. No. 53 (fig. 8), 

which contained as much as 39 ppm arsenic and 140 

ppm zinc. The association of these two metals suggests 

that the rocks in this locality contained sphalerite. 

Small-scale stratigraphic variation (82

x) is large in 

the carbonate units, except in the Sauk, and reflects 

compositional layering within stratigraphic intervals 

of about 100 m or less. Together with the sampling and 

- 5 1 :3 20 - 30 4:4 <5 - 7 1:4 

.J50 1 :3 310 - 870 4:4 170 -260 4:4 

- 15 2:3 15 - 30 4:4 <10 0:4 

0:3 5 - 15 4:4 <5 0:4 

.3 2:3 .1 .6 4:4 <.1 .2 3:4 

- 7.0 3:3 19 - 30 4:4 44 -47 4:4 

-300 3:3 100 - 200 4:4 <7 - 7 2:4 ~00 3:3 1500 - 300 4:4 70 -150 4:4 

0:3 30 - 70 4:4 <7 0:4 

0:3 10 - 15 4:4 <10 0:4 

0:3 1.5 4:4 <1 0:4 

- 15 2:3 ll - 30 4:4 <10 0:4 

-50 3:3 50 - 200 4:4 20 -150 4:4 

analytical variance (82

" +82 £), the three components collectively account for over one-half of the total observed 

variance in more than half of the elements listed in 

tables 6-9. However, only for organic carbon, sodium, 

selenium, strontium, and zinc in one or more sampled 

units did analytical variance (82£, table 5) form more 

than half of the three variances combined. Thus, the 

largest part of the total geochemical variability in 

these rocks represents a small-scaled interstratification of rock layers composed of differing proportions of 

the major rock-forming constituents calcite, dolomite, 

quartz, and "clay." For the most part, the three combined variances estimate the basic geochemical im-
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F27 

TABLE 12.-Geochemical summary of rocks of the Kaskaskia sequence in Missouri and adjacent States 

[GM, geometric mean, except as noted; GD, geometric deviation, except as noted; Ratio, number of samples in which element detected to total number of samples; ppm, parts per million; 

leaders (---) indicate no data available] 

Element 

GM GO Ratio GM GO Ratio 

Ag, ppm------

A 1 , percent--

As, ppm------

8, ppm-------

Ba, ppm------

<0.5 0:40 <510.5 0:30 1.72 4:30 

3.04 11:30 

1:30 

5.72 27:30 

<.53 9:40 .83 

.83 2.58 17:40 .57 

<20 2:40 <20 

6.4 6.79 37:40 4.0 

Be, ppm------

C, carbonate, 

percent---- 111 

C, organic, 

percent---- .22 1 Ca, percent-- 32 

Cd, ppm------ <1 

0:40 

2 1.69 40:40 

2.31 34:40 2 8.96 40:40 

1:40 

<1 

.23 136 

<1 

0:30 

2 1.42 30:30 

2.41 25:30 2 6.7 30:30 

0:30 

Ce, ppm------ <150 0:40 <150 0:30 

Co, ppm------ <3 2:40 <3 1 :30 Cr, ppm------ 9.4 3.27 38:40 7.7 3.22 28:30 

2.56 11:30 

17:30 

Cu, ppm------ .85 2.04 20:40 .62 

F, ppm------- 38 6.01 27:40 360 

Fe, percent--

Ga, ppm------

Hg, ppm------

K, percent---

La, ppm------

L i, ppm------

Mg, percent--

Mn, ppm------

Mo, ppm------

Na, percent--

.15 3.71 30:40 

<5 2:40 

.030 2.37 38:40 

.077 2.83 21 :40 

<30 11:40 

• 78 3.87 5:40 

.56 5.98 40:40 160 2.05 40:40 

<3 3:40 

.017 2.63 38:40 

Nb, ppm------ <1 0 

Nd, ppm------

Ni, ppm------ 2. 3 

0:40 

2.43 11:40 

6 .• 35 17:40 

5:40 

P, ppm------- 92 

Pb, ppm------ <1 0 

.10 3.24 20:30 

<5 1 :30 

.029 2.36 28:30 

.051 3.41 12:30 

24 1.20 8:30 

<5 2:30 

.23 2.19 30:30 150 2. 11 3 0 : 30 

.34 3.85 2:30 

.015 2.38 28:30 

<10 

2.0 

200 

<10 

0:30 

2.24 6:30 

3.90 16:30 

1 :30 

Dolomite only 

GM 

<0.5 .46 

1.1 

<20 

24 

.21 12] 

<1 

<150 

<3 

17 

1.9 

120 

GO Ratio 

0:10 2.68 5:10 

2.74 6:10 

1 :10 

3.73 10:10 

0:10 

2 1.69 10:10 

1.85 9:10 2 5.17 10:10 

1:10 

0:10 

1:10 2.64 10:10 

2.18 9:10 

3.49 10:10 

.60 1.95 10:10 

<5 1 :10 .036 1.95 10:10 

.34 3.19 9:10 

24 1.19 3:10 

<5 3:10 1

8.1 2 1.62 10:10 

220 1.38 10:10 

<3 1 :10 

.026 1.69 10:10 

<10 

3. 9 

<220 

6.5 

2.30 

2.34 

0:10 

5:10 

1:10 

4:10 

GM 

<O. 5 4.4 

6.4 

64 

220 

4 1.1 

1.2 

.27 

3.4 

<1 

<150 

4.8 4 130 

.3 

1400 

1.8 

16 

.39 

2.2 

30 

Bus hburg, Sands tone 

and Syl amore Sands tone 

Shale Chert Chattanooga Shale Member of Chattanooga 

Shale 

GD Ratio GM GD Ratio Observed range Ratio Observed range Ratio 

3:18 <0. 5 0:20 <0.5 0:4 <0.5 1.64 18:18 

2.22 18:18 

1. 73 18:18 

2.15 18:18 

<.53 

<1 

1 :20 5.3 - 8.5 4:4 <.53 - .53 

7:20 

39 1.80 18:20 50 - 100 4:4 <20 - 50 

23 l. 52 20: 20 300 - 500 4:4 10 - 30 

1.64 12:18 2.0 4:4 <1 

7. 77 18:18 

3.89 16:18 

6.59 17:18 

<1 

3 .06 

0:20 

13:20 

1.5 -

.01 -

1.0 -

< .071-

<1 

.08 4:4 <.01 - 5.2 

.44 

3 .86 

<1 

2.26 20:20 

15:20 

0:20 

4.3 4:4 .2 - .4 

.21 2:4 <.071- 19 

2:18 0:4 <1 

2:18 <150 0:20 <150 0:4 <150 

1.91 18:18 <3 0:20 7 - 15 4:4 <3 - 3 2.28 18:18 2.8 2.62 20:20 70 - 100 4:4 3 - 7 

2.83 18:18 1.1 2.02 12:20 50 - 70 4:4 1 - 3 

3.23 18:18 <10 6:20 

1.58 18:18 

1.81 18:18 

3.09 17:18 

1.56 18:18 

.081 1.96 10:20 2.2 - 3.3 4:4 <.07 -

<5 0:20 <5 

.017 2.28 18:20 

(.083 2:20 

14:18 <30 1:20 

20 - 30 4:4 

.02 - .42 4:4 

3.1 - 4.3 4:4 

30 - 70 4:4 

<.01 -

<.08 -

<30 

.42 

.02 

.16 

0:4 

1:4 

3:4 

4:4 

0:4 

3:4 

4:4 

2:4 

0:4 

4:4 

1:4 

4:4 

4:4 

3:4 

0:4 

3:4 

2:4 

0:4 

25 1.84 18:18 2.8 2.01 6:20 25 - 38 4:4 <5 - 9 2:4 

4:4 

4:4 1.6 2.62 18:18 3 .012 17:20 .80 - l. 1 4:4 

140 2.05 18:18 49 4.38 20:20 50 - 150 4:4 

<3 6:18 <3 0:20 3 - 30 4:4 

<10 

<70 

21 4

300 

11 

.088 2.16 18:18 .013 1.71 19:20 

3:18 <10 

3:14 <70-

2.23 18:18 <5 

2.95 13:18 <220 

1.58 13:18 <10 

0:20 <10 

0:1 <70 

1 :20 30 

8:20 <130 

2:20 10 

.15- .24 4:4 

- 10 - 70 

- 70 

- 310 

- 20 

1 :4 

2:4 

4:4 

3:4 

4:4 

.03 - 3.5 

10 -300 

<3 .007-

<10 

<5 

170 

<10 

- 7 

-870 

- 15 

0:4 

.014 4:4 

0:4 

1 :4 

4:4 

2:4 

Sc, ppm------ <5 3:40 

2.28 32:40 

.22 

.19 

.70 

5.24 2:30 

2.53 24:30 5.59 19:30 

3.17 30:30 

<5 

.20 

3.5 

88 

190 

1:10 8.2 1.60 17:18 

3.47 18:18 1.40 18:18 

1.87 18:18 

<5 

.11 1 44 

8.1 209 

0:20 10 - 15 4:4 

4:4 

4:4 

4:4 

4:4 

<5 0:4 

3:4 

4:4 

4:4 

4:4 

Se, ppm------ .19 2.38 8:10 4 .64 1.76 12:20 .6 - 1.4 <.1 - .3 

Si, percent-- 1 .1 4.53 28:40 

3.62 40:40 

4.22 9:10 23 33.07 20:20 27 - 30 24 - 46 

Sr, ppm------ 270 

Ti, ppm------ 1 70 

390 

318 1.45 10:10 150 2.55 16:20 70 - 100 7 -150 

34:40 24:30 5.18 10:10 4 2300 4 1.76 18:18 5.15 20:20 3000 -7000 70 -150 

v. ppm------- y, ppm-------

Yb, ppm------

Zn, ppm------

Zr, ppm------

7. 5 

17 

.85 

19 

6. 7 

1 Arithmetic mean 2Standard deviation. 3Median. 

4See table 16. 

2.11 25:40 

1.97 34:40 

1.69 18:40 

1.68 38:40 

4.79 18:40 

6.1 

17 

• 78 

21 

5.2 

2.53 16:30 

1.84 26:30 

1.73 13:30 

1.39 30:30 

3.69 11:30 

12 

6 

.86 

15 

20 

2.24 

1.84 

2.23 

2.67 

4.45 

9:10 

8:10 

5:10 

8:10 

7:10 

precision which would be encountered in representing 

a carbonate outcrop by one sample, if that sample were 

analyzed by the methods listed in table 4 or by 

methods of similar precision. 

The element averages listed for carbonate rocks in 

tables 10-13 estimate the most probable concentration 

to be expected in a randomly selected carbonate 

sample from an outcrop in the study area. Because of 

the marked control on concentration of some elements 

by rock type (limestone versus dolomite), a summary 

for both types is given when appropriate. A summary 

of the combined rock types is also given for those 

elements whose variation is relatively independent of 

carbonate mineralogy. A number of elements-barium, 

cobalt, chromium, copper, iron, potassium, lithium, 

phosphorus, silicon, strontium, titanium, and zirconium-show levels of concentration of five times or 

120 

25 

- 300 

- 50 

- 15 - 15 4 2.3 

55 

95 

1.87 18:18 

1.87 18:18 

1.93 18:18 

3.09 18:18 

2.00 18:18 

<7 

<10 

<1 

<10 

<10 

0:20 

1 :20 

0:20 

5:20 

3:20 

200 

20 

3 

87 

100 

5 

- 120 

- 150 

4:4 

4:4 

4:4 

4:4 

4:4 

<7 

<1 

<1 

<10 

20 

- 25 

-150 

2:4 

2:4 

0:4 

2:4 

4:4 

more in dolomite compared to limestone in the same 

unit. The presence of potassium, titanium, and zirconium in this list suggests that the dolomitic rocks 

tend to be more clay rich than the limestones. 

The data in tables 10-13 show that, even in 

limestone or dolomite, element concentration may 

vary within rather wide limits depending upon what 

unit is being studied. Both the dolomite and the 

limestone of Pennsylvanian age tend to be more element rich than similar rocks in the underlying units. 

The Pennsylvanian dolomite is particularly rich in 

iron, manganese, and phosphorus; and the Pennsylvanian limestone is particularly rich in barium, 

chromium, copper, iron, manganese, and silicon. These 

differences reflect the fact that carbonate in the Pennsylvanian rocks is everywhere admixed with considerable noncarbonate detritus. 
F28 GEOCHEMICAL SURVEY OF MISSOURI 

TABLE 13.-Geochemical summary of rocks of Pennsylvanian age in Missouri and adjacent States 

[GM, geometric mean, except as noted; GD, geometric deviation, except as noted; Ratio, number of samples in which element detected to total number of samples; ppm, parts per million; 

leaders (--1 indicate no data available) 

Element 

or ash 

Ag, ppm-------

Al, percent---

As, ppm-------

Ash, percent--

B. ppm--------

GM 

<0.5 

8.5 

9.0 

72 

Ba, ppm-------- 430 

Northern area 

Southern area Be, ppm------- 1.7 

C, carbonate, 

percent------ .16 

C, organic, 

percent------

Ca, percent---

Cd, ppm-------

Ce, ppm-------

.32 

1.1 

<1 

<150 

Co, ppm------- 12 

Northern area 

Southern area 

Cr, ppm------- 95 

Northern area 

Southern area 

Cu, ppm-------

F, ppm--------

Northern area 

Southern area 

Fe, percent---

Northern area 

Southern area 

23 

700 

3.8 

Shale 

GO Ratio GM 

0:32 

1.24 32:32 

2.11 32:32 

1.34 32.32 

1. 48 32:32 

<0.5 

3.1 

4.0 

38 

Sandstone 

GO Ratio 

0:30 

2.46 30:30 

2.31 27:30 

1.78 26:30 

240 1.48 14:14 

16:16 

14:30 

120 1. 74 

1.44 31:32 1.0 1.46 

5.07 31:32 .010 

2. 57 

4.15 

27:32 .34 

32:32 .22 

0:32 <1 

9:32 <150 

1.67 32:32 

11 

4.4 

1.26 32:32 33 

2.61 

1.66 

1. 50 

32:32 

32:32 

32:32 

8.1 

200 

56 

2. 7 

1.4 

1. 97 

5.09 

22:30 

30:30 

24:30 

0:32 

10:30 

1.66 14:14 

2.59 13:16 

2.35 30:30 

2. 57 

2.25 

4.39 

1.71 

1.86 

30:30 

14:14 

13:16 

14:14 

16:16 

Ga, ppm-------

Ge, ppm-------

Hg, ppm-------

K, percent----

La, ppm-------

30 1.45 32:32 

0:32 

30:32 

32:32 

32:32 

11 1.94 27:30 

<1 0 <10 .045 2.60 .015 2.12 

0:32 

22:30 

29:30 

24:30 

2.7 1.29 .49 3.47 49 1.37 34 1.65 

L i, ppm-------

Mg, percent---

Mn, ppm-------

Mo, ppm-------

Na, percent---

Nb, ppm-------

Nd, ppm-------

Ni, ppm-------

Northern area 

Southern a rea 

79 

.95 

170 

<3 

.50 

7. 7 

<70 

38 

p. ppm-------- 610 

Northern area 

Southern area 

Pb, ppm------- 17 

Sc, ppm------- 15 

Se, ppm------- .46 

Si, percent--- 27 

Sr, ppm------- 200 

Ti, ppm------- 4200 

V, ppm-------- 140 

y. ppm------- 30 

Northern area 

Southern area 

Zn, ppm------- 82 

Zr, ppm------- 110 

1 Arithmetic mean. 2 Standatd deviation. 3 Computed for raw. 

1.48 32:32 17 

1.45 32:32 .20 

1.97 32:32 260 

0:32 

1.67 32:32 

<3 

.33 

1.25 11:32 9.0 

11:32 <70 1.50 32:32 

31 

11 

1.89 32:32 570 

1.92 30:32 15 

1.26 32:32 7.2 

3.63 

1.15 

1.65 

1.41 

1.36 

29:32 .12 

32:32 139 

32:32 83 

32:32 2400 

32:32 39 

1.61 32:32 22 

3.3 

1. 7 

1.47 32:32 32 

1.48 32:32 190 

2.38 29:30 

4.40 30:30 

4.54 30:30 

4:30 

7.05 30:30 

1.22 18:30 

8:24 

2.22 14:14 

2.69 13:16 

2.11 28:30 

1.81 27:30 

1.43 24:30 

3.15 

2 4.09 

3. 73 

2.84 

1.45 

17:30 

30:30 

30:30 

30:30 

30:30 

1.69 26:30 1.48 14:14 

1.86 13:16 

2.77 25:30 

2.20 30:30 

Combined data for 

1 imestone and dolomite 

GM 

<0.5 

.44 

2.5 

<20 

44 

<1 

.10 1 31 

<1 

<150 

1.3 

12 

20 

3. 5 

100 

.96 

GO Ratio 

0:32 

2.50 16:32 

2.95 27:32 

1 :32 

3.01 32:32 

1 :32 

21.37 32:32 

2. 77 19:32 

2 8.18 32:32 

2.32 

0:32 

3.24 12:32 

1.84 16:16 

1.77 16:16 

2.14 32:32 

3.46 29:32 

2.49 32:32 

2.2 2.34 8:32 

<10 0:32 

.030 2.96 30:32 

.16 2.52 28:32 

24 1.20 5:32 

2.6 2.93 11:32 

.67 4.11 32:32 

830 2.37 32:32 

<3 3:32 

.045 2.43 32:32 

<10 

<70 4.3 

180 

690 

4.2 

<5 

< .31 

2.9 

990 

180 

15 

0:32 

0:4 

2.24 17:32 

3.68 8:16 

2.29 16:16 

3.13 9:32 

4:32 

2.69 29.32 

2.98 32:32 

3.86 32:32 

3.16 32:32 

2.29 29:32 

8.0 2.39 15:32 

24 2.32 31 :32 

14 2.28 25:32 

Limestone only Dolomite only 

GM 

<0.5 

.36 

2.2 

<20 

42 

<1 

llJ 

.10 134 

<1 

<150 

<3 

12 

19 

3.3 

83 

.82 

1.5 

<1 0 

.032 

.14 

14 

<5 .48 

680 

1.9 

.041 

<10 

<70 4.4 

380 

550 

3.5 

.55 

.31 

2.4 

1400 

160 

13 

6. 5 

24 

12 

GO Ratio 

0:28 

Observed 

range 

2.58 12:28 

3.01 23:28 

0.53-

2 

1.6 

8.3 

0:28 <20 20 

2.61 28:28 30 - 300 

1:28 

21.03 28:28 6.6 - 10 

3.18 

2 3.77 

17:28 

28:28 

1:28 

0:28 

<.1 -

11 

• 7 

16 

<1 1 

8:28 

1.84 16:16 

1. 90 1 2: 12 20 30 

1.79 28:28 2 15 

3.85 25:28 240 - 290 

1.97 28:28 2.2- 3.7 

2.80 

2. 78 

2.42 

1.93 

5:28 

0:28 

26:28 

24:28 

5:28 

<5 

.01-

.17-

7:28 5 13 

.04 

.58 

2.27 28:28 6.3 - 8.4 

1.86 28:28 2000 - 7000 

1.28 3:28 

2.24 28:28 .03- .17 

2.32 

0:28 

0:4 

15:28 

3.68 8:16 

<5 -

2.18 12:12 870 - 1700 

3.57 7:28 <10 15 

4.48 4:28 

2.56 

2.46 

2.13 

2. 73 

2.05 

26:28 

28:28 

28:28 

28:28 

25:28 

.3 - .9 

8.4 - 17 

70 - 150 

300 - 700 

30 50 

2.43 11:28 20 30 

2.22 27:28 17 

1.89 21 :28 50 

37 

70 

Ratio 

0:4 

4:4 

4:4 

1:4 

4:4 

0:4 

4:4 

2:4 

4:4 

1:4 

0:4 

4:4 

4:4 

4:4 

4:4 

4:4 

4:4 

3:4 

0:4 

4:4 

4:4 

0:4 

4:4 

4:4 

4:4 

0:4 

4:4 

0:4 

2:4 

4:4 

GM 

<0.05 

• 75 

4.2 

10 

25 

25 

1.6 

<15 

<1 

<15 

3.4 

g,1 

22 

72 

1.9 

Coal 

GO Ratio 

14:30 

1.85 30:30 

2.87 30:30 

1.84 30:30 

2.24 30:30 

2.24 30:30 

1.40 30:30 

3:15 30:30 

5:20 

1:30 

3.04 30:30 

1 .81 30:30 

2.21 

1.63 

2.65 

30:30 

30:30 

30:30 

15 1.82 2g:30 

30:30 

30:30 

11:30 

.093 1.75 

.15 2. 78 

<3 

5.1 2.82 

.036 1.96 

22 2.31 

1.8 3.07 

.013 1.81 

30:30 

30:30 

30:30 

26:30 

30:30 

<1 0:30 

20 2.99 30:30 

<220 6:30 

2:4 48 2.94 30:30 

0:4 2.0 1.96 29:30 

3:4 

4:4 

4:4 

4:4 

4:4 

4:4 

4:4 

4:4 

1.9 

1.7 

22 

320 

13 

1.95 

2.15 

1.51 

2.44 

1.97 

30:30 

30:30 

30:30 

30:30 

30:30 

6.3 2.20 29:30 

22 4.39 30:30 

11 2.24 29:30 

In summary, the dominant control on geochemical 

variation in carbonate rocks of this study is the 

distribution of constituent calcite, dolomite, quartz, 

and "clay." The distribution of these constituents is 

highly variable at local scales and results in a very 

large geochemical heterogeneity within or among 

closely spaced carbonate outcrops. This heterogeneity 

arises for the most part from local compositional interlayering in the rocks. Imprinted upon this local 

variability is a weak but discernible regional 

geochemical difference that reflects a tendency for carbonate of Pennsylvanian age to be richer in most trace 
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F29 

elements than the older carbonates. Variation at broad 

scales within the bedrock units is similarly weak and 

largely reflects variation in dolomite content. The upper Sauk is discernibly less dolomitic (slightly more 

argillic) than the lower Sauk; and scattered sections of 

Tippecanoe, Kaskaskia, and Pennsylvanian carbonate 

rocks are distinctly more dolomitic than others. 

SHALE 

Shale is considered in this study to include all varieties 

of fine-grained detrital sedimentary rock containing 

large amounts of clay minerals, whether the rock is 

fissile or not. Shale underlies extensive parts of 

50 

"Clay" 

Quartz 

xPH15 

6 

xPH13 

6 xPHOl 

0 x PH25 

000 

PH02X 

50 

western and northern Missouri and eastern Kansas as 

it forms a major part of the Pennsylvanian rocks and a 

minor part of the Kaskaskia rocks (fig. 3). Throughout 

most of this area it tends to be covered by glacial 

deposits; nevertheless, it is an environmentally important part of the landscape in west-central Missouri, 

eastern Kansas, and northeastern Oklahoma, where it 

forms a prominent parent material of soil. In addition, 

it is intimately associated with large deposits of strippable coal in Missouri, Kansas, and Oklahoma. 

The normative mineral compositions of 62 samples 

of shale are compared in figure 10. The norms were 

computed as for the carbonate rocks, except that only 

MgO in excess of 2 percent was put into dolomite. The 

0 MH07 

oMHlO oMH06 

MH18o oMH05 

6TH05 

DMHOl 6TH01 

XPH26 ° MH09 

0 MH14 

oMH13 oSH04 

0 MH17 

50 

Calcite+ dolomite 

FIGURE 10.-Normative mineralogy of shale samples of the Sauk sequence (circle), the Tippecanoe sequence (triangle), the Chattanooga 

Formation (closed square), the Kaskaskia sequence (open square), and of Pennsylvanian age (X). Numbered samples are referred to in 

text. 
F30 GEOCHEMICAL SURVEY OF MISSOURI 

pattern in figure 10 suggests the following: (1) shale 

in this study generally contains between 30 and 80 percent normative quartz, contains between 5 and 50 percent normative clay, and exhibits a quartz-clay ratio 

consistently greater than 1.0; (2) shale in the Pennsylvanian rocks is rarely calcareous (exceptions are 

PH01, PH02, PH13, PH15, PH25, and PH26); (3) shale 

in the Kaskaskia is distinctly calcareous, with 10 of 17 

samples (MH01, MH05-MH07, MH09, MH10, MH13, 

MH14, MH17, and MH18) containing more than 25 

percent normative calcite plus dolomite; all of the 

dolomitic shales of this sequence (MH01, MH06, 

MH07, MH09, and MH10) were collected in Missouri; 

and (4) shale in the Sauk and Tippecanoe is dolomitic 

(particularly SH04, TH01, and TH05). 

Results of the analysis of variance for shale of the 

Kaskaskia sequence and of Pennsylvanian age are 

given in tables 14 and 15, and summary statistics are 

given in tables 12 and 13. The total geochemical 

variability (S2

1og x) in shale of the Kaskaskia sequence 

is notably larger than that in shale of Pennsylvanian 

age, except for lead. This parallels the situation found 

in the carbonate studies, in which units having the 

larger area of outcrop tended to be more geochemically 

uniform. In the carbonate study, this situation largely 

reflected a sample mix of nearly pure limestone and 

dolomite (in the units with the larger variability). Here 

the increase in variation reflects more a variable admixture of calcite and dolomite minerals in the 

samples of shale of the Kaskaskia sequence (fig. 10). 

Statistically significant variation in the major rockforming elements (aluminum, carbonate carbon, 

calcium, magnesium, and silicon), which reflects variation in the distributions of "clay," calcite, dolomite, 

and quartz, occurs largely within stratigraphic sections (S2

9+S2

x) in shale of Pennsylvanian age, but 

occurs between sections (S2 p+S2 v) in shale of the 

Kaskaskia sequence. Between-area variation (S2 p) in 

shale of the Kaskaskia sequence is statistically significant for half of the elements in table 14 and reflects a 

tendency for shale units in the Kaskaskia, which occur 

as isolated lenses or formations, to be more or less 

geochemically distinct. In Missouri, these formations 

tend to be highly calcareous (low aluminum, high carbonate), whereas in Oklahoma and Arkansas, they 

tend to be more aluminous and less calcareous. 

Area averages in shale of the Kaskaskia sequence 

were examined for stability by the criterion described 

previously. Es was computed by: 

Es= S2v +S2'1+S2c 

2 4 (15) 

The pertinent parameters for this examination are 

listed below: 

Element v nr Er Es 

Aluminum .................... 0.93 5 0.0048 0.0091 

Boron ........................ .49 8 .0048 .0141 

Barium ....................... .67 6 .0111 .0167 

Berbllium .................... 1.32 4 .0050 .0050 

Car on, org ................... .62 7 .0307 .0787 

Chromium .................... 3.90 3 .0087 .0087 

Iron ......................... 1.83 4 .0035 .0040 

Gallium ...................... .66 6 .0067 .0151 

Potassium .................... .49 8 .0031 .0061 

Sodium ...................... 1.50 4 .0112 .0143 

Nickel ........................ .55 7 .0125 .0326 

Phosphorus .................. 1.57 4 .0476 .0476 

Scandium .................... 1.10 5 .0039 .0072 

Selenium ..................... 6.78 3 .0125 .0109 

Titanium ..................... 2.20 4 .0047 .0047 

Vanadium .................... .87 5 .0079 .0144 

Ytterbium .................... 1.81 4 .0073 .0073 

TABLE 14.-Components of logarithmic variance estimated for shale 

of the Kaskaskia sequence 

[Asterisk (*), value significantly greater than zero at the 0.05 probability level) 

Variance 

Total Between areas Be tween sections Be tween samp 1 es 

Element 1 oglO 

variance 

( ~og x l Percent Percent Percent Component of Component of Component of 

(S~) total (S~) total (S~+ S~) total 

Al---------- 0.0466 *0.0224 48 0.0123 27 0.0119 25 As---------- .1204 .0291 24 * .0762 63 .0151 13 B----------- .0569 *.0187 33 .0182 32 .0200 35 Ba---------- .1111 * .0445 40 0 <1 .0666 60 Be---------- .0460 * .0262 57 0 <1 .0198 43 

C, carbonate . 7927 .4899 62 * .2273 29 .0755 9 

C, organic-- .3485 *.1333 38 .0994 29 .1158 33 Ca---------- .6702 .2229 33 * .3313 49 .1160 17 

Co---------- .0794 .0282 36 0 <1 .0512 64 

Cr---------- .1278 * .1017 80 .0086 7 .0175 14 

Cu---------- .2044 .1422 70 *. 0387 19 .0235 11 

F----------- .2595 0 <1 .0280 11 .2315 89 Fe---------- .0399 *. 0258 65 .0019 5 .0122 31 Ga------ ---- .0669 * .0267 40 .0203 30 .0197 30 Hg---------- .2407 .0009 <1 * .1916 80 .0481 20 

~----------- .0369 * .0121 33 .0123 33 .0124 34 

La---------- .0452 .0067 15 .0204 45 .0180 40 L i---------- .0695 .0137 20 *. 0323 46 .0235 34 Mg---------- .1745 .1026 59 *. 0563 32 .0156 9 Mn---------- .0977 .0505 52 * .0276 28 .0196 20 

Na---------- .1113 *.0667 60 .0124 11 .0322 29 Ni---------- .1358 * .0482 36 .0426 31 .0450 33 P----------- .4905 *. 3000 61 0 <1 .1905 39 

Pb---------- .0397 0 <1 * .0323 81 .0074 19 

Sc---------- .0411 *.0215 52 .0090 22 .0107 26 

Se---------- .2916 * .2541 87 .0059 2 .0316 11 

Si---------- .0217 0 <1 *.0163 75 .0054 25 Sr---------- .0745 0 <1 * .0463 62 .0282 38 Ti---------- .0604 * .0415 69 0 <1 .0189 31 

V----------- .0737 * .0342 46 .0180 24 .0215 29 

y ----------- .0738 .0242 33 0 <1 .0496 67 

Yb---------- .0815 * .0525 64 0 <1 .0290 36 Zn---------- .2401 .1530 64 *.0616 26 .0255 10 

Zr---------- .0910 .0242 27 * .0444 49 .0224 25 
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F31 

TABLE 15.-Components of logarithmic variance estimated for shale of Pennsylvanian age 

[Asterisk(*}, value significantly greater than zero at the 0.05 probability level] 

Total Between areas Between sections 

Element 1 oglO 

variance 

2 Percent Percent (SLog x) Component of Component of 

(S2) total (S2) total 

B y 

Al---------- 0.0086 o.o > 1 o.o <1 

As---------- .1045 .0040 4 .0175 17 

B----------- .0164 .0003 2 0 <1 

Ba---------- .0293 .0008 3 0 <1 

Be---------- .0250 0 <1 0 <1 

C, carbonate .6206 0 <1 0 <1 

C, organic-- .1679 0 <1 0 <1 

Ca---------- .3821 0 <1 0 <1 

Co---------- .0499 .0003 1 0 <1 

Cr---------- .0097 0 <1 0 <1 

Cu---------- .1733 .0266 15 0 <1 

F----------- .0490 .0085 17 0 <1 

Fe---------- .0306 .0022 7 0 <1 

Ga---------- .0258 0 <1 0 <1 

Hg---------- .1727 0 <1 0 <1 

K----------- .0125 0 <1 0 <1 

La---------- .0183 0 <1 0 <1 

Li---------- .0292 0 <1 0 <1 

Mg---------- .0259 .0006 2 0 <1 

Mn---------- .0865 .0325 38 *.0123 14 

Na---------- .0494 *.0210 43 0 <1 

Ni---------- .0312 0 <1 0 <1 

P----------- .0770 *.0275 36 .0131 17 

Pb---------- .0806 0 <1 0 <1 

Sc---------- .0097 .0022 23 0 <1 

Se---------- .3138 .0095 3 0 <1 

Si---------- .0037 0 <1 0 <1 

Sr---------- .0470 .0044 9 0 <1 

Ti---------- .0225 0 <1 0 <1 

V----------- .0178 0 <1 0 <1 

Y----------- .0425 *.0112 26 .0015 4 

Yb---------- .0304 .0034 11 .0008 3 

Zn---------- .0276 .0005 2 0 <1 

Zr---------- .0288 0 <1 .0004 1 

The area averages for beryllium, chromium, 

phosphorus, selenium, titanium, and ytterbium are 

sufficiently stable (Es~r) to be computed using the 

available data. These averages are given as medians in 

table 16. The tendency for shale in this sequence to be 

geochemically distinct by formation is apparent from 

these medians. Clearly, the differences in phosphorus 

and titanium are controlled almost entirely by exceptionally high phosphorus and exceptionally low 

titanium in shale of the Choteau Limestone. Just as 

clearly, differences in selenium are controlled by the 

Variance 

Be tween dec i 1 es Between percentiles Be tween samp 1 es 

Percent Percent Percent 

Component of Component of Component of 

(S~) total (S2) total (s2 + s2) total K n £ 

*0.0025 29 0.0017 20 0.0044 51 

*.0363 35 0 <1 .0467 45 

0 <1 *.0088 53 .0074 45 

0 <1 *.0200 67 .0088 30 

*.0087 35 0 <1 .0163 65 

.2960 48 *.1732 28 .1513 24 

0 <1 *.0825 49 .0854 51 

.1964 51 * .1129 30 .0728 19 

.0061 12 .0067 13 .0369 74 

*.0048 49 .0012 12 .0037 38 

*.0349 20 .0351 20 .0766 44 

.0160 33 *.0157 32 .0087 18 

0 <1 .0093 30 .0192 63 

.0044 17 .0061 24 .0154 60 

.0466 27 *.0852 49 .0408 24 

*.0041 33 .0028 23 .0056 45 

0 <1 *.0126 69 .0057 31 

.0014 5 *.0167 57 • 0111 38 

*.0057 22 .0075 29 .0121 47 

0 <1 .0133 15 .0284 33 

*.0203 41 .0049 10 .0032 6 

0 <1 .0027 9 .0286 91 

0 <1 *.0202 26 .0163 21 

*.0361 45 .0027 3 .0418 52 

0 <1 *.0046 47 .0029 30 

* .1344 43 .0568 18 .1132 36 

.0002 7 *.0018 48 .0017 45 

.0053 11 .0147 31 .0025 48 

0 <1 *.0154 68 .0071 32 

0 <1 *.0102 57 .0076 43 

0 <1 .0104 24 .0194 46 

0 ·<1 *.0174 57 .0088 29 

0 <1 .0087 31 .0186 67 

.0045 16 *.0129 45 .0110 38 

high concentrations in samples from Arkansas. Both 

the Fayetteville Shale (3.2, 9.0 ppm) and the Ruddell 

Shale Member (3.2, 4.8 ppm) of the Moorefield Formation are high in selenium here. Additional data are 

needed if the area averages for the remaining elements 

are to be computed. 

Between-section variance (S2 y) within the areas of the 

Kaskaskia also reflects at least in part the erratic 

distribution of geochemically distinct formations. For 

example, two organic-rich samples taken from the 

Fayetteville Shale at loc. No. 43 (fig. 7) contained 5 per-
F32 GEOCHEMICAL SURVEY OF MISSOURI 

TABLE 16.-Geochemical medians for selected elements in areas of 

shale of the Kaskaskia sequence 

[Data are in parts per million) 

Area---------------

Nunber of samples--

localities (fig.? ) 30, 31 33 34, 35 38, 39 41, 43 

Warsaw Fayetteville 

Geologic formations and and Ruddell 

Hannibal Choteau Northview Fayetteville(?) Shale Member! 

Element: 

Beryll iun 1.5 <1 <1 

Chromi un 100 50 130 85 300 

Phosphorus 220 5500 <220 410 370 

Seleniun .3 .35 .45 .35 4.0 

Ti tanilJll 3000 850 2500 2000 4000 

Ytterbium 2.5 1.5 

1 Of Moorefield Fonnation. 

cent or more organic carbon as well as some of the 

highest trace element concentrations measured in 

shale during this study. Sample MH20 contained 

3 ppm silver, 5 ppm cadmium, 700 ppm chromium, 150 

ppm lanthanum, 1. 7 percent phosphorus, 500 ppm 

vanadium, and 150 ppm yttrium; and sample MH19 

contained 3 ppm beryllium, 50 ppm gallium, and 250 

ppm zinc. The relatively high phosphorus in MH20 

suggests that this sample is probably high in apatite. 

Three elements in shale of Pennsylvanian age (sodium, 

phosphorus, and yttrium) exhibit statistically significant between-area variance (S2 

11). Averages for these 

areas were examined for stability by the methods 

previously described. E s was computed from equation 

14. The pertinent parameters for this examination are 

as follows: 

Element nr Er Es 

Sodium ...................... 0.74 6 0.0047 0.0051 

Phosphorus .................. .56 7 .0067 .0101 

Yttrium ...................... .36 10 .0031 .0033 

Additional data are required if area averages for these 

elements are to be computed. 

Stratigraphic variation (S2

9+S2 x) is large in shale of 

Pennsylvanian age, with all but eight elements exhibiting statistically significant variation at these 

levels of the design. The larger scaled stratigraphic 

variance (S2

9) in aluminum, arsenic, beryllium, 

chromium, copper, potassium, manganese, sodium, 

lead, and selenium reflects a tendency for shale 

samples taken low in the section (loc. Nos. 58, 60, 63, 

64, and 65, fig. 8) to be slightly higher in these 

elements than samples taken higher in the section (loc. 

Nos. 59, 61, 62, 53, and 66). In fact, samples PH01 and 

PH04 (both from loc. No. 58) contained 200 ppm copper and 12 ppm selenium, respectively, the highest 

measured values in shale of the study, and well above 

the average concentrations in these rocks of 23 ppm 

copper and 0.46 ppm selenium (table 13). The presence 

of sodium in this suite of elements suggests that this 

variation could be reflecting, in part, a variation in 

feldspar content of the shales. 

Variation between percentiles (S2 x) is the dominant 

scale of geochemical variability in shales of Pennsylvanian age and reflects compositional interlayering 

within stratigraphic intervals of about 100 m or less. 

Together with sampling and analytical variance 

(S2

" +S2 

~J, the three components collectively account for 

over half of the total observed variance in 27 of 34 entries listed in table 15, although for eight elements the 

analytical variance (S2n table 5), forms more than half 

of the three components combined. (The eight elements 

are beryllium, chromium, fluorine, sodium, 

phosphorus, scandium, ytterbium, and zinc.) Still, like 

the carbonate rocks, the largest part of the total variation in Pennsylvanian shale is quite local and reflects 

differences among closely spaced beds. For the most 

part, the three combined variances estimate the basic 

geochemical imprecision which would be encountered 

in representing an outcrop of Pennsylvanian shale by a 

single sample, if that sample were analyzed by the 

methods listed in table 4. 

The component of stratigraphic variability in shale 

of the Kaskaskia sequence is contained in the betweensample variance (S2 "), because each stratigraphic section is represented by two samples collected from 

throughout the section (table 1). In contrast to the carbonates and the Pennsylvanian shales, the combined 

sampling-stratigraphic and analytical variance (S2

+S2 £) 

in this unit is not the most prominent part of the total 

variance. Nevertheless, for many elements, the absolute value of these combined components is comparable to the combined geochemical imprecision 

(S2 x +S2

" +S2 £) in the Pennsylvanian shale, so that the 

imprecision encountered in representing shale outcrops by one sample each is roughly equal for the two 

units. Nine elements in shale of the Kaskaskia sequence exhibit an analytical component (S2

n table 5) 

which forms more than half of this imprecision: boron, 

beryllium, fluorine, mercury, sodium, lead, scandium, 

selenium, and zirconium. 

The element averages for shale (tables 12, 13, and 16) 

are estimates of the most probable concentration to be 

expected in a randomly collected shale sample from an 
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F33 

outcrop in the study area. Shales of the Kaskaskia contain at least twice the calcium and carbonate carbon of 

the shale of Pennsylvanian age, reflecting the relatively calcareous nature of the Kaskaskia. These shales 

also contain less than half of the aluminum found in 

shale of Pennsylvanian age, indicating considerably 

less clay material in the Kaskaskia. Shale of Pennsylvanian age is consistently higher in all other 

elements compared, except for chromium, fluorine, 

magnesium, and selenium. 

In summary, geochemical variability is greater in 

shales of the Kaskaskia sequence than in shales of 

Pennsylvanian age and reflects a highly variable admixture of carbonate material. This variability 

manifests itself partly as differences among the 

numerous shale formations which tend to crop out in 

different areas, and partly as differences between 

closely spaced organic-rich and organic-poor beds. 

Although shale of Pennsylvanian age tends to be more 

geochemically uniform overall than shale in the 

Kaskaskia, it is distinctly richer in trace elements 

because it is a more clay rich unit. 

Quartz 

X 

X 

~ PS23x 0 

PS26 X SS18 0 

SANDSTONE AND CHERT 

Sandstone is abundant only in the Pennsylvanian 

outcrops of northeastern Oklahoma and in a few local 

areas in southeastern Missouri where sandstone in the 

Roubidoux Formation is well developed (fig. 3). The 

general paucity of sandstone over large parts of the 

study area makes it of less environmental interest than 

carbonate or shale, although water supplies are locally 

drawn from sandstones of Pennsylvanian age and strip 

mining of coal in Missouri has brought sandstone to 

the surface where it may form a conspicuous part of 

the newly formed land surface. Chert is prominent in 

outcrop as both nodules and interlayers in strata of 

Mississippian age; but, being chemically inert, it is 

resistant to weathering and has little effect on the local 

geochemical environment. 

The normative mineral compositions of 86 samples 

of sandstone and chert are compared in figure 11; the 

normative minerals were computed as for the shales. 

Sandstones of Pennsylvanian age are mostly mixtures 

of quartz and clay, except for four moderately 

---------

0 

x 5 SSl4o 

PS25 X SS17 MS02 0 

/'\ r / General compositional 

50 

SS15° 

MSOl 

0 

0 

/ range of shale of 

Pennsylvanian age SS16 ° 50 X "Clay" (.:..:...._.-:.x:..:..__ ____ ----,-------~ Calcite+ 

10 lO dolomite 5 

50 

"Clay" [___----------------,~-------------~dolomite Calcite+ 

FIGURE 11.-Normative mineralogy of sandstone of the Sauk sequence exclusive of the Roubidoux Formation (circle), from the Roubidoux 

Formation (dot), the Tippecanoe sequence (triangle), and the Kaskaskia sequence (solid square), from Pennsylvanian rocks (X), and from 

chert of the Kaskaskia sequence (open square). Numbered samples are referred to in text. 
F34 GEOCHEMICAL SURVEY OF MISSOURI 

calcareous sandstones (PS09, PS23, PS25, and PS26). 

Mineralogically, most of the sandstones can be viewed 

as quartz-rich shales, and Pennsylvanian sandstone 

and shale together tend to form a normative quartzclay compositional continuum from near zero to about 

50 percent clay (fig. 11). In contrast, lower Paleozoic 

sandstones tend to form a quartz-carbonate continuum. The most calcareous of these lower Paleozoic 

sandstones are five samples from the Sauk sequence 

(SS14-SS18), including two of the Roubidoux Formation (SS17, SS18), and two samples of the Mississippian Bushberg Sandstone (MS01, MS02). Chert of the 

Kaskaskia sequence is normatively similar to the lower 

Paleozoic sandstones because it is pervasively mixed 

with appreciable calcite. 

Results of the analysis of variance for these units are 

given in tables 17-19, and summary statistics are 

given in tables 10, 12, and 13. Sandstones of the 

Roubidoux are much more variable in magnesium 

(mostly in dolomite) and silicon (mostly in quartz) than 

are the cherts in the Kaskaskia or the sandstones of 

Pennsylvanian age and reflect the spotty occurrence of 

admixed dolomite in the Roubidoux samples from loc. 

Nos. 20 and 21 (fig. 4). The chert samples are more 

variable in carbonate carbon and calcium (mostly in 

calcite) than are the sandstones of Pennsylvanian age, 

but overall (in contrast to the carbonates and shales), 

the total observed variance (S2

1og x) in the trace 

elements is not notably larger in any one unit. 

Between· area variance (S2 p) is large in sandstone of 

Pennsylvanian age, compared with sandstone in the 

Roubidoux Formation and chert in the Kaskaskia sequence. Eleven elements in Pennsylvanian sandstone, 

nine of them trace elements and two elements in sandstones of the Roubidoux, exhibit statistically signifiTABLE 17.-Components of variance estimated for sandstone of the 

Roubidoux Formation 

[Variance calculated on data transformed to logarithms, except as noted. Asterisk (*), 

value significantly greater than zero at the 0.05 probability level] 

Variance 

Total Between areas Between sections Between samples 1 og 

10 

Element variance 

2 Percent Percent Percent (\og xl Component of Component of Com~onent of 

(S~) total (S~) total (S +S2) total 

n E 

Ba-------- 0.0803 o.o <1 0.0095 12 0.0708 88 

C, organic .2462 0 <1 .0980 40 .1482 60 Cr-------- .1540 0 <1 *.1168 76 .0372 24 Cu-------- .1087 0 <1 .0283 26 .0804 74 Mg-------- 1.2534 .4084 33 .3852 31 .4598 37 

Mn-------- .2847 * .1187 42 .0336 12 .1323 46 

~~1::::::: 139:6~~; *.0500 31 0 <1 .1124 69 42.0284 30 72.8832 52 24.1776 17 Sr-------- .1210 .0212 18 0 <1 .0998 82 

Ti-------- .5629 0 <1 .3204 57 .2425 43 Zr-------- .0450 .0008 2 0 <1 .0442 98 

1variance calculated on nontransformed data. 

TABLE lB.-Components of variance estimated for chert of the 

Kaskaskia sequence 

[Variance calculated on data transformed to logarithms, except as noted. Asterisk (*), 

value significantly greater than zero at the 0.05 probability level] 

Variance 

Total Between areas Between sections Between samples 

Element log 

variance 

(S~og xl Percent Percent Percent 

Component of Component of Component of 

(S~} total (S~} total (S~ + S~) total 

B----------- 0. 0650 o.o <1 0.0287 44 0.0363 56 

Ba---------- .0330 .0030 9 .0069 21 .0232 69 

C, carbonate 1.1036 0 <1 * .6276 57 .4760 43 

C, organic-- .1250 0 <1 .0608 49 .0642 51 

Ca---------- .8685 0 <1 * .6032 69 .2653 31 

Cr---------- .1747 0 <1 .0915 52 .0832 48 

Hg---------- .1286 0 <1 *. 0827 64 .0459 35 

Mg---------- .7287 0 <1 .3876 53 .3411 47 

Mn---------- .4115 0 <1 .1514 37 .2601 63 

~~~========= .0541 .0103 19 0 <1 .0438 81 

20.1129 0 <1 9.7411 48 10.3718 52 

Sr---------- .1653 0 <1 .0719 43 .0934 57 

Ti ---------- .5077 0 <1 .2674 53 .2403 47 

lvariance calculated on nontransformed data. 

cant variation at this level. Averages for the areas 

were examined for stability by the methods previously 

described. Es for Pennsylvanian sandstone was computed from equation 14, andEs for the Roubidoux was 

computed from equation 15. The pertinent parameters 

for this examination are as follows: 

Element nr Er Es 

Roubidoux Formation 

Manganese ................... 0.72 6 0.0277 0.0499 

Sodium ······················ .44 9 .0125 .0281 

Pennsylvanian Sandstones 

Boron ........................ .15 20 .0028 .0071 

Barium ....................... .71 6 .0099 .0089 

Cobalt ······················· .63 7 .0078 .0053 

Fluorine ...................... .49 8 .0261 .0258 Iron ......................... .51 8 .0089 .0085 

Potassium .................... .79 6 .0203 .0212 

Lithium ...................... .45 9 .0111 .0148 

Nickel ........................ .46 8 .0152 .0133 

Strontium .................... .59 7 .0293 .0356 

Titanium ..................... .31 11 .0143 .0182 

Ytterbium .................... .58 7 .0067 .0052 

Area averages for barium, cobalt, fluorine, iron, nickel, 

and ytterbium in Pennsylvanian sandstone are sufficiently stable (Es~r) when computed from the 

available data to be listed separately in table 13. Additional data are required if the area averages for theremaining elements are to be computed. This variation 

reflects compositional differences in sandstone from 

the northern (Kansas and Missouri) and southern areas 

of outcrop (fig. 8). The variation in potassium suggests 

that sandstone in the northern area is higher in clay 

material than sandstone in the southern area. 
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F35 

TABLE 19.-Components of variance estimated for sandstone of Pennsylvanian age 

(Variance calculated on data transformed t.o logarithms. except as noted. Asterisk 1•1. value significantly greater than zero at the 0.05 probability level) 

Total Between areas Between sections 

Element loglO 

variance 

2 Percent Percent (Slog X} Component of Component of 

(S2} total (S2} total 

s y 

Al---------- 0.1531 0.0390 26 o.o <1 

As---------- .1320 0 <1 .0278 21 

B----------- .0630 *.0080 13 .0060 9 

Ba---------- .1025 *.0424 41 0 <1 

C, carbonate .6493 .0042 1 0 <1 

C, organic-- .0870 0 <1 0 <1 

Ca---------- .0500 .0172 3 0 <1 

Co---------- .0890 *.0343 39 0 <1 

Cr---------- .1380 .0222 16 0 <1 

Cu---------- .1676 .0273 16 .0340 20 

F----------- .3107 * .1 022 33 0 <1 

Fe---------- .1077 *.0365 34 0 <1 

Ga---------- .0834 .0117 14 0 <1 

Hg---------- .1071 0 <1 .0183 17 

K----------- .2186 *.0968 44 0 <1 

La---------- .0470 .0123 26 0 <1 

Li---------- .1451 *.0452 31 0 <1 

Mg---------- .4136 .1237 30 0 <1 

Mn---------- .4313 0 <1 0 <1 

Na---------- .7190 .1683 23 0 <1 

Nb---------- .0072 .0012 17 0 <1 

Ni---------- .1771 *.0555 31 0 <1 

P----------- .1049 .0130 12 0 <1 

Pb---------- .0658 0 <1 *.0176 27 

Sc---------- .0244 0 <1 .0005 2 

sil _________ 35.8132 6.4903 18 0 <1 

Sr---------- .3266 *.1216 37 0 <1 

Ti---------- .2059 *.0483 23 0 <1 

V----------- .1405 .0182 13 0 <1 

Y----------- .0522 .0109 21 0 <1 

Yb---------- .0739 *.0272 37 .0005 1 

Zn---------- .1958 0 <1 0 <1 

Zr---------- .1174 .0218 19 .0014 1 

1variance calculated on nontransformed data. 

Between-section variation (S2 y) in the siliceous rocks 

is relatively small. Statistically significant variation at 

this scale is exhibited only by chromium in sandstones 

of the Roubidoux; lead in th~ Pennsylvanian sandstones; and carbonate carbon, calcium, and mercury in 

the Kaskaskia chert. The variation in carbonate carbon 

and calcium in the Kaskaskia reflects the variation in 

admixed calcite in the chert. Mercury tends to be high 

in samples with low calcite. Lead was unusually high in 

two samples of Pennsylvanian sandstone collected 

from the southernmost traverse (fig. 8). Sample PS27 

(loc. No. 74) contained 150 ppm lead and PS31 (loc. No. 

Variance 

Between deciles Between percentiles Between samples 

Percent Percent Percent 

Component of Component of Component of 

(S2} total (S2} total (S2 +S2} total 6 K n E 

0.0577 38 *0.04371 29 0.0126 8 

.0042 3 .0058 4 .0942 71 

0 <1 .0159 25 .0332 53 

.0189 18 .0272 27 .0131 14 

0 <1 *.4724 73 .1728 27 

.0168 19 0 <1 .0702 81 

0 <1 *.3367 67 .1457 29 

0 <1 *.0296 33 .0249 28 

0 <1 *.0994 72 .0164 12 

0 <1 *.0787 47 .0275 16 

0 <1 * .1209 39 .0876 28 

.0054 5 *.0493 46 .0165 15 

.0282 34 *.0312 37 .0123 15 

0 <1 .0360 34 .0527 49 

.0512 23 *.0641 29 .0064 3 

*.0242 51 0 <1 .0105 22 

.0316 22 *.0416 29 .0267 18 

* .1663 40 *.0687 16 .0587 14 

.0445 10 *.2813 65 .1 055 25 

*.4102 56 .0210 3 .1286 18 

*.0039 54 0 <1 .0021 29 

.0056 3 *.0743 42 .0418 24 

0 <1 .0241 23 .0678 65 

0 <1 .0012 2 .0470 71 

0 <1 .0075 31 .0164 67 

12.0215 34 *9.0786 25 8.2227 23 

.0967 30 *.0740 23 .0343 11 

.0238 12 .0616 30 .0722 35 

.0445 32 *.0613 44 .0166 12 

0 <1 *.0330 63 .0084 16 

0 <1 *.0324 44 .0137 19 

*.0896 46 .0258 13 .0804 41 

0 <1 *.0725 62 .0217 18 

66) contained 50 ppm, in contrast to an average concentration of 11 ppm in these rocks (table 13). 

Large-scale stratigraphic variation (S2e) in sandstones of Pennsylvanian age is moderate. Statistically 

significant variation is exhibited by lanthanum, 

magnesium, sodium, niobium, and zinc. The variation 

in sodium probably reflects mostly variation in 

feldspar, and the variation in magnesium might reflect 

variation in the type of clay material. Geochemical 

variation between percentiles (S2 x) is marked in sandstone of Pennsylvanian age and reflects, to a large 

degree, the distribution of calcareous sandstone in-
F36 GEOCHEMICAL SURVEY OF MISSOURI 

terlayered through stratigraphic intervals of about 

100m or less. Calcium and carbonate carbon each exhibit over half of their total variance at this level, and 

the sta~istically significant variation in the remaining 

18 entnes of the table probably also reflects this variation in admixed calcite. 

Variation at the lowest levels (S2 

I( +S2 

11 +S2 £) is large in 

all three units, accounting for over half of the total 

observed variation in more than half of the entries 

listed in tables 17-19. Only for boron, organic carbon, 

manganese, niobium, and sodium in one or more of the 

sampled units did analytical variance (S2£, table 5) form 

more than half of the total variation at these three 

levels. Thus, like the variability of the carbonate rocks 

and the Pennsylvanian shale, the largest part of the 

total geochemical variation in the sandstone and chert 

represents a small-scaled interstratification of compositionally differing beds. In the Pennsylvanian sandstones this difference appears to be due almost solely 

to variable amounts of contained calcite. As in the 

other stratified units of this study, the three combined 

variances estimate the basic geochemical imprecision 

which would be encountered in representing an outcrop 

of sandstone or chert by one sample, if that sample 

were analyzed by the methods listed in table 4. 

The averages listed for sandstone in tables 10 and 

13, and for chert in table 12, are estimates of the most 

probable concentration to be expected in a randomly 

collected sample from an outcrop in the study area. 

Sandstone in the Roubidoux Formation and chert in 

the Kaskaskia sequence both are highly siliceous and 

poor in trace elements. Sandstones of Pennsylvanian 

age are relatively rich in trace elements due to their 

argillic content, and those in the northern part of the 

outcrop area tend to be more argillic than those in the 

southern part. Practically every element listed for 

sandstone or chert is higher in sandstones of Pennsylvanian rocks than in the two older units. Most show 

average concentrations 5-10 times those in the 

Kaskaskia chert or the Roubidoux sandstones. As with 

the carbonates and shales, variability between closely 

spaced beds of sandstone is large and reflects the 

presence or absence of calcareous interbeds. 

GRANITE AND RHYOLITE 

The igneous rocks are of the least environmental 

significance of all the units studied owing to their 

restricted area of occurrence, their general resistance 

to weathering, and their limited supplied of potable 

ground water. Locally, they contain a few large 

deposits of economic minerals including iron ore 

(Hayes and Guild, 1967). 

All of the samples collected in this part of the study 

are granitic, and their gross compositional variation is 

largely controlled by feldspar variation. The 60 

samples are compared in figure 12 on the basis of their 

normative feldspar composition. All calcium was put 

into anorthite, all sodium into albite, and all potassium 

into orthoclase. The rhyolite (extrusive) samples are 

much more variable in normative feldspar than are the 

granite (intrusive) samples, and include the most 

albite-rich (PC06) as well as the most orthoclase-rich 

(PC18) samples. 

Normative anorthite is highest in samples from loc. 

Nos. 2 (PC03), 3 (PC06), 14 (PC28), 22 (PC43), and 23 

(PC46), which are alined in a northwest direction 

across the central part of the Precambrian outcrop 

area (fig. 3). Nine samples, all of them rhyolite, are 

distinctly high in normative orthoclase-PC09 and 

PC10 (loc. No. 5), PC16 (loc. No. 8), PC17 through 

PC20 (loc. Nos. 9 and 10), and PC25 and PC26 (loc. No. 

13). Four of these five localities are alined in a westerly 

direction acrosss the outcrop (fig. 3). This alinement in 

both anorthite and orthoclase may reflect structural 

features of some sort. From imagery studies, Lowell, 

Osburn, and Roth (1977) noted the existence of both a 

pronounced N.45 W./N.45 E. structural pattern and a 

subordinate north-south/east-west lineament set in 

southeast Missouri. 

Results of the analysis of variance for the Precambrian rocks are given in table 20, and summary 

statistics are given in table 21. Only beryllium and zirconium show statistically significant differences 

between the two rock types (S2 y). This difference in 

beryllium reflects the unusually low concentrations 

measured in the high-potassium rhyolites (table 21). 

The between-locality variance (S2

9) accounts for the 

largest part of the geochemical variation in these 

rocks; 23 of 28 elements exhibit statistically significant variation at this level of the sampling design, and 

14 of the 28 exhibit 75 percent or more of the total 

observed variation at this level. Included in these 23 

elements are most of the major rock-forming elements: 

aluminum, calcium, iron, potassium, magnesium, 

sodium, and titanium. Thus, variation at this scale 

reflects mostly simple variation in mineral composition. Some portion of this variance is apparently 

regionally controlled as Sides (1977) noted the presence 

of linear trends in these rocks for the oxides of silicon 

aluminum, iron, potassium, calcium, and titanium. H~ speculated that these trends may reflect tilting of the 

igneous mass to the southwest, with subsequent 

deeper erosion to the northeast. 

In contrast to the sedimentary rocks, the sampling 

and analytical variance (S2 

11 +S2 £) tends to be relatively 

small in the igneous rocks. Only fluorine, mercury, 
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F37 

Albite 

PC46 

PC06 A PC28 A PC43 0 0 A PC03 

.6.0 ~ 

.6. 

0 

Anorthite 

PC16 A 

Orthoclase 

PC25 

A APC26 

FIGURE 12.-Normative anorthite, albite, and orthoclase in samples of granite (circle) and rhyolite (triangle). Numbered samples are 

referred to in 'text. 

TABLE 20.-Components of variance estimated for igneous rocks of 

Precambrian age 

[Variance calculated on data transformed to logarithms, except as noted. Asterisk (*~. 

value significantly greater than zero at the 0.05 probability level] 

Element 

Al-----

As-----

Ba-----

Be-----

Ca-----

Cu-----

F------

Fe-----

Ga-----

Hg-----

K------

La-----

Mg-----

Mn-----

Na-----

Nb-----

Nd-----

P------

Pb-----

Se-----

Se-----

Si 1----

Sr-----

Ti-----

Y------

Yb-----

Zn-----

Zr-----

Total 

log 

variance 

2 

Between granite 

and rhyolite 

(\og xl 

0.0013 

.2401 

.1317 

.0418 

.2313 

.1082 

.2642 

.0272 

• 0042 

.0615 

.0106 

.0334 

.2113 

• 1369 

.1202 

0.0 

.0092 

0 

* .0084 

.0268 

.0038 

0 

0 

< .0001 

0 

.0008 

0 

.0055 

0 

.0149 

.0140 .0004 

.0149 0 .1993 0 .0321 .0007 

.1197 ,o 

.0532 

3.7226 

.1144 

.0499 

.0194 

.0117 

.1104 

.0608 

0 

0 

0 

0 

0 

.0006 

0 

*.0118 

Percent of 

total 

<1 

4 

<1 

20 

12 

4 

<1 

<1 

<1 

<1 

7 

<1 

3 

<1 

12 

3 

<1 

<1 

2 

<1 

<1 

<1 

<1 

<1 

<1 

5 

<1 

19 

Varia nee 

Between localities 

*0.0010 

*.2193 

*.1079 

* .0242 

*.1801 

* .0863 

.0134 

* .0261 

*.0024 

.0181 

*.0088 

* .0169 

*.1870 

* .1033 

*.1 027 

0 

* .0049 

*.1410 

*.0137 

* .1047 

.0033 

*2.6402 

*.1092 

*.0415 

*.0087 

* .0040 

* .0995 

.0061 

Percent 

of 

total 

78 

91 

82 

58 

78 

80 

5 

96 

57 

29 

83 

51 

88 

75 

85 

<1 

33 

71 

43 

87 

6 

71 

95 

83 

45 

34 

90 

10 

1Variance calculated on nontransformed data. 

Between samples 

Component 

(S~ + S~) 

0.0003 

.0115 

.0239 

.0093 

.0243 

.0181 

.2508 

.0011 

.0018 

.0434 

.0011 

.0165 

.0188 

.0336 

.0026 

.0135 

.0100 

.0583 

.0177 

.0150 

.0499 

1.0824 

.0052 

.0084 

.0107 

.0071 

.0109 

.0428 

Percent of 

total 

22 

5 

18 

22 

10 

16 

95 

4 

43 

71 

10 

49 

9 

25 

2 

97 

67 

29 

55 

13 

94 

29 

4 

17 

55 

61 

10 

70 

niobium, neodymium, lead, selenium, yttrium, ytterbium, and zinc exhibit more than half their total 

observed variance at these two levels combined. For 12 

of the 28 entries in table 20, the analytical variance 

(S2 f:' table 5) accounts for more than half of this sum. 

Thus, the geochemical imprecision which would be encountered in representing a granite or rhyolite outcrop 

by one sample (if that sample were analyzed by the 

methods listed in table 4) would be considerably less 

for most elements in these rocks than in the sedimentary rocks. 

Overall, the igneous rocks are more similar in their 

trace element content to the shale and sandstone in the 

study area than they are to the limestone or dolomite 

(table 21 versus tables 10-13), although for copper, 

lithium, and vanadium, the reverse appears to be true . 

Sodium is consistently higher in the igneous rocks, 

regardless of which sedimentary lithology is used, and 

chromium is consistently lower . 

ECONOMIC MATERIALS 

The economic geology of Missouri is briefly summarized in Stout and Hoffman (1973). Major products 

include limestone, dolomite, shale, granite, coal, iron, 

lead-zinc-copper sulfide ore, and oil and gas. Although 

coal and lead-zinc-copper ore constitute only a small 

fraction of the total mass of rocks studied, they are 

both materials of great environmental importance. 
F38 GEOCHEMICAL SURVEY OF MISSOURI 

TABLE 21.-Geochemical summary of igneous rocks of Precambrian 

age in Missouri 

[GM, geometric mean, except as noted; GD, geometric deviation, except as noted; Ratio, 

number of samples in which element detected to total number of samples; ppm, parts 

per million; leaders(-·) indicate no data available] 

Combined data, except as indicated, 

Element for granite and rhyolite of Potassium-rich rhyolite only 

typical composition 

GM GD Ratio GM GD Ratio 

Al, percent 6.7 1.08 51 :51 6.4 1.11 9:9 As, ppm---- 2. 9 2.20 48:51 14 5.82 9:9 B, ppm----- 14 1.22 7:51 17 1.37 4:9 Ba, ppm---- 560 2.37 51:51 830 1.51 9:9 Be, ppm 

Granite-- 2.0 1.48 29:30 Rhyolite- 1.8 1.35 21 :21 .80 l. 73 4:9 

Ca, percent .35 2. 59 50:51 <.071 3:9 Ce, ppm---- 140 1.15 38:51 130 1.20 5:9 Co, ppm---- <3 13:51 <3 0:9 Cr, ppm---- .64 3.44 22:51 .67 4.21 4:9 Cu, ppm---- 1.9 2.22 43:51 1.1 3.39 5.9 F, ppm----- 380 3.54 48:51 290 2.99 9:9 

Fe, percent 1. 7 1.49 51 :51 1.8 1.15 9:9 Ga, ppm---- 29 1.10 51 :51 24 1.31 9:9 Hg, ppm---- .015 1.84 43:51 .012 2.15 6:9 K, percent- 4.2 1.16 51 :51 7 .o 1.08 9:9 La, ppm---- 60 1.45 50:51 42 1.66 8:9 L i, ppm---- 3.1 3.48 26:51 1.5 4.94 3:9 

Mg, percent .080 2. 92 51 :51 .049 2.19 9:9 Mn, ppm---- 310 2.39 51 :51 280 1.88 9:9 Mo, ppm----- <3 17:51 <3 0:9 Na, percent 2.8 1.15 51 :51 .51 3.31 9:9 Nb, ppm---- 11 1.32 45:51 11 1.22 9:9 Nd, ppm---- 76 1.32 46:51 72 1.45 7:9 

Ni, ppm---- <5 2:51 <5 0:9 

P' ppm----- 280 3.06 35:51 1220 6:9 Pb, ppm---. 19 1.48 51 :51 18 1.67 9:9 Sc, ppm---- 5. 7 2.55 36:51 4.4 2.05 6:9 Se, ppm---- .l 0 2.02 30:51 .051 33.14 3:9 Si, percent "35 1 1.31 51 :51 :'35 1.34 9:9 

Sn, ppm---- <1 0 l :51 <10 0:9 

Sr, ppm---- 74 2.20 51 :51 61 1.94 9:9 Ti, ppm---- l ,3000 1. 70 51 :51 1,100 1.37 9:9 v, ppm---- 4.5 5.05 22:51 <10 2:9 y, ppm---- 69 1.34 51 :51 63 l. 56 9:9 

Yb, ppm---- 7.1 1.27 51 :51 8.2 1.31 9:9 Zn, ppm---- 50 2.12 51 :51 31 1.93 9:9 Zr, ppm 1 Granite-- 140 1.56 30:30 150 

Rhyolite- 220 1.47 21 :21 170 2.32 9:9 

1Median. 

-'Arithmetic mean. 3Standard deviation. 

Both contain a large number of trace elements in extraordinarily high concentrations which are introduced 

into the near-surface environment upon mining, processing, and use. 

COAL 

Thirty samples of coal are compared in figure 13 on 

the basis of three normative minerals and percent combustible material (hydrocarbons) in the raw coal. Percent combustibles were calculated as 100 minus the 

percent ash, normative pyrite was calculated from percent total iron, and clay and quartz were calculated as 

for the sedimentary rocks. Four samples contained 

more than 1 percent calcium in the raw coal (C12, C16, 

C18, C24-two Tebo, one Mulky, and one Lexington 

sample), suggesting that a few samples may contain a 

calcium-bearing mineral. The normative compositions 

provide no obvious basis for classification of Missouri 

coal, although samples from the Rowe, Drywood, 

Mineral(?), and Weir-Pittsburg coal beds are consistently higher in ash than samples from the Tebo, 

Lexington, and Mulky coals. 

Results of the analysis of variance are giveJ;t in table 

22, and summary statistics are given in table 13. 

Between-bed variation (S2 y) is statistically significant 

for a number of environmentally important elements, 

particularly for two of the more volatile 

elements-arsenic and mercury. Eleven of twenty-one 

elements exhibit statistically significant variation between beds, although constituents of the detrital fraction (aluminum and silicon) do not. A major cause of 

bed-to-bed variation appears to be the spotty occurrence of pyrite (or marcasite). Normative pyrite ranges 

from 0.6 percent (C23, C24, the Mulky coal) to 14.9 percent (C11, Tebo coal). 

Sphalerite was observed in one sample (C16, Tebo 

coal) which contained over 7000 ppm zinc and 37 ppm 

TABLE 22.-Components of logarithmic variance estimated for coal 

of Pennsylvanian age 

[Asterisk(*), value significantly greater than zero at the 0.05 probability level] 

Variance 

Total Between coal bedsl Between samples 

E1 ement loglO 

or ash variance 2 Percent Percent (\og xl Component of Component of 

(S~) total (s; +S~) total 

AI------ 0.0722 0.0230 32 0.0429 68 

As------ .2148 * .1294 60 .0854 40 

Ash----- .0708 .0261 37 .0447 63 

B------- .1025 * .0936 91 .0099 9 

Ba------ .1319 0 <l .1319 100 

Be------ .0218 .0069 31 .0149 69 

Ca------ .2505 .0696 28 .1809 72 

Co------ .2393 * .1739 73 .0654 27 

Cr------ .0669 .0027 4 .0642 96 

Cu------ .1197 .0332 28 .0866 72 

F------- .0456 .0036 8 .0420 92 

Fe------ .1841 * .1499 81 .0341 19 

Ge------ .0716 *.0326 46 .0390 54 

Hg------ .0597 * .0295 49 .0302 51 

K------- .2166 0 <l .2116 100 

L i------ .2052 .0644 31 .1407 69 

Mg------ .0916 0 <I .0916 100 

Mn------ .1326 .0277 21 .1049 79 

Mo------ .2203 *.1784 81 .0419 19 

Na------ .0662 .0093 14 .0569 86 

Ni------ .2320 *.1832 79 .0487 21 

Pb------ .2232 * .1234 55 .0998 45 

Sc------ .0863 .0240 28 .0623 72 

Se------ .0843 .0135 16 .0708 84 

Si------ .1116 .0171 15 .0945 85 

Sr------ .0325 .0026 8 .0298 92 

Ti ------ .1669 0 <l .1669 100 

V------- .0881 .0255 29 .0625 71 

y ------- .1198 * .0937 78 .0262 22 

Zn------ .4234 * .2924 69 .1310 31 

Zr------ .1259 .0152 12 .1107 88 

1see table 3 for names of coal beds. 
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F39 

100 ° 

BK 

K K 

B 

K figure 13 

l T 

TL 

T T 

90 10 

A Pyrite 

B 

·~ 

;; ~ B ~ ~ T ~ 

-:1!! SM B ~)( ·~ 

~ ~ D ";S:)::i AM ~ .. $ " D 

M 

M 

s 20 80 

B 

w 

w 

T 

30 JOL-----------------------~----------------------~L-----------------------~0 

30 20 Pyrite 10 

FIGURE 13.-Comparison of samples of coal on the basis of three normative minerals and percent of combustible material 

(computed as 100 minus percent ash). Coal beds are: B, Bevier; D, Drywood; L, Lexington; K, Mulky; M, Mineral(?); R, 

Rowe; S, Summit; T, Tebo; W, Weir-Pittsburg. 

cadmium. Hatch and others (1976) noted the 

widespread, but erratic, distribution of sphalerite 

through coals of southeast Iowa, Missouri, arid 

southeast Kansas (as much as 1.9 percent zinc and 175 

ppm cadmium in raw coal). The sphalerite occurs in 

vertical cracks as much as 1.5 em wide. Other elements 

exhibiting important bed-to-bed variation, such as 

arsenic, cobalt, mercury, nickel, lead, and perhaps 

germanium and molybdenum, may also reflect in part 

the distribution of sulfide minerals. 

Average concentrations of many elements in raw 

Missouri coal are roughly similar to concentrations in 

the enclosing sedimentary rocks (table 13) or even to 

the underlying rocks (tables 10-12). Among the common rock-forming elements, aluminum, potassium, 

and silicon are present in coal in about the same 

amounts as in carbonates, and calcium is present in 

about the same amount as in sandstone or chert. 

Magnesium and phosphorus are notably lower in coal 

than in the common sedimentary rock types; and only 

germanium, mercury, lead, and zinc appear to be consistently higher in raw coal (on the average) when compared to non-coal rocks in the study area. The highest 

individual trace-element concentrations observed were 

50 ppm arsenic (C30, Summit coal), 48 ppm cobalt 

(COl, Rowe coal), 49 ppm germanium (Cl'S, Lexington 

coal), 177 ppm nickel (Cll, Tebo coal), and 318 ppm 

lead (C30). 

Sampling and analytical variance (S2

" +S2 £) are large 

for many elements, particularly barium, chromium, 

fluorine, potassium, magnesium, strontium, and 

titanium. The analytical component (S2£, table 5) ac-
F40 GEOCHEMICAL SURVEY OF MISSOURI 

TABLE 23.-Concentrations of elements in samples of crushed and pulverized ore, lead concentrate, zinc concen· 

District and typical concentrations in 

[Concentrations are in percent, parts per million (ppm), 

Sample No., median Element 

or type of 

surficial material Ag Al As Ba Ca Cd Co Cr Cu F Fe Ga Ge Hg In 

(ppm) (percent) (ppm) (ppm) (percent) (ppm) (ppm) (ppm) (percent) (ppm) (percent) (ppm) (ppm) (ppb) (ppm) 

Crushed ore 

1 30 0.3 160 50 16 170 150 0.4 140 4.3 <5 <10 50 <10 

lR 50 .5 240 30 15 190 200 • 7 70 6.8 <5 15 80 <10 

Pulverized ore 

2 2 0.5 12 30 20 16 70 10 0.04 120 3.9 <5 <10 20 <10 

2R 1 .5 9.5 30 21 16 100 10 .05 130 3.9 <5 <10 50 <10 

3 5 1. 21 70 17 35 150 7 .2 150 3.1 <5 <10 10 <10 

3R 5 1. 22 70 17 36 100 7 .2 150 3.1 <5 <10 30 <10 

4 15 .5 48 50 20 110 200 10 .3 130 1. 7 <10 20 <10 

4R 10 .5 52 70 20 110 70 20 .3 120 1.7 <5 <10 30 <10 

5 10 .3 62 50 20 110 200 7 .3 90 1.8 <5 <10 <10 <10 

5R 10 .3 54 70 20 110 100 7 .3 90 1.8 <10 10 <10 

6 20 .3 100 20 18 130 150 3 .4 80 4.8 <5 <10 30 <10 

6R 20 1. 100 15 17 130 100 3 .4 90 4.6 <5 10 60 <10 

7 10 .5 35 30 20 140 100 7 .1 50 1.9 <5 <10 50 <10 

7R 7 .3 42 30 20 140 70 3 .1 50 1.9 <5 <10 <10 <10 

8 30 .5 99 50 18 350 200 10 .2 130 2.0 <5 <10 20 <10 

8R 50 .3 88 20 19 330 150 7 .2 90 2.0 <5 <10 10 <10 

Median 10 .5 50 40 19 110 100 7 .2 110 2.0 <5 <10 20 <10 

Lead concentrate 

9 100 0.1 53 20 0.50 210 1,500 150 0.3 <10 3.3 <5 <10 240 <10 

9R 100 .15 55 10 .50 200 2,000 150 .3 10 3.3 <5 <10 260 <10 

10 70 .1 69 15 .53 250 1,000 20 1.8 10 3.2 <5 20 130 <10 

lOR 50 .15 65 15 .60 250 1,500 30 2.0 <10 3.5 <5 20 110 <10 

11 200 .2 330 10 .52 330 1,000 20 1. 7 <10 4.3 <5 20 80 <10 

llR 200 .15 330 20 .52 310 1,000 20 1.7 <10 4.4 <5 20 90 <10 

12 70 .1 190 15 .92 360 500 30 .6 <10 1.4 <5 <10 90 <10 

12R 70 .15 180 15 .90 350 500 30 .6 <10 1.3 <5 <10 80 <10 

13 100 .15 220 10 .86 160 700 2 .4 10 3.3 <5 10 100 <10 

13R 100 .1 240 10 .86 240 500 3 .4 <10 3.4 <5 <10 80 <10 

14 70 .07 140 10 .96 320 500 2 .9 <10 1.4 <5 15 140 <10 

14R 100 .1 160 10 .90 290 700 2 1. 50 1.4 <5 15 60 <10 

15 50 .1 260 10 .40 160 1,000 2 1.3 <10 2. 7 <5 15 80 <10 

15R 50 .1 250 5 .43 160 1,000 5 1.3 <10 2.9 <5 15 80 <10 

Median 85 .13 190 10 .56 250 1,000 20 .95 <10 3.4 <5 15 90 <10 

Zinc concentrate 

16 700 0.2 100 15 1.9 6,300 700 10 1.6 20 7.8 15 30 230 <10 

l6R 500 .2 100 50 2.0 6,400 1,000 15 1.8 70 7.7 30 140 <10 

17 1,000 .2 140 70 1.5 7,800 500 7 .9 40 3.6 50 50 <10 

17R 1,000 .2 150 15 1.5 8,200 500 7 .9 50 3.6 70 30 210 <10 

18 300 .3 260 30 2.4 7,600 700 15 1.5 60 2.2 30 200 50 

l8R 700 .15 220 15 2.4 7,600 1,000 15 1.2 10 2.6 50 30 120 50 

19 500 .1 170 7 1.1 7,100 1,000 1 .6 50 2.4 70 150 100 50 

l9R 700 .1 170 10 1.2 7,100 700 1 .6 20 2.4 70 150 110 50 

20 500 .07 240 10 • 70 9,000 1,000 5 .6 <10 1.9 70 20 150 <10 

20R 500 .07 220 10 .68 8,600 700 5 • 7 <10 1.8 100 20 160 20 

21 700 .1 160 10 1.5 6,800 500 1 .4 <10 2.0 70 70 90 20 

21R 500 .1 150 30 1.5 6,700 500 2 .4 50 1.9 70 240 50 

Median 600 .13 170 13 1.5 7,100 700 6 .8 50 2.5 70 30 150 20 

Copper concentrate 

22 50 0.2 480 30 .19 170 20,000 150 26 <10 15 <5 100 210 150 

22R 70 .07 440 20 .19 180 20,000 200 27 50 17 <5 100 280 200 

23 30 .05 330 10 .21 120 7,000 50 28 <10 19 <5 300 180 150 

23R 20 .05 330 10 .25 110 5,000 70 27 <10 15 <5 200 210 70 

24 70 .05 1,900 5 .21 92 7,000 300 29 <10 18 <5 200 200 70 

24R 50 .03 2,000 5 .22 88 10,000 200 28 <10 17 <5 150 200 150 

25 30 .15 >2 ,300 70 .47 230 7,000 100 27 30 19 200 100 100 

25R 50 .05 2,200 5 .48 230 10,000 150 26 <10 15 <5 200 150 70 

26 50 .2 >2 ,300 70 .26 94 5,000 5 28 20 18 200 120 150 

26R 100 .05 2,500 7 .25 94 5,000 10 28 <10 18 <5 150 170 150 

Median 50 .05 2,000 10 .24 120 7,000 130 29 <10 18 <5 200 190 150 

Mill tailings 

27 10 0.3 59 30 20 30 70 0.1 160 4.5 <5 <10 30 <10 

27R 10 .3 63 20 20 25 100 .1 110 4.8 <5 <10 30 <10 

Typical concentrations in surficial materials in southeast Missouri 

Cultivated soils 

(Tidball, 1974)-- <1 3.8 8.4 510 0.20 <1 11 52 151 270 2.0 11 38 

Uncultivated soils 

(Erdman and 

others, 1976a, 

12 1 table 6)-········ <1 2.1 6. 7 340 .065 <1 9.5 30 160 1.5 5.9 45 

Carbonate res idullll 

(U.S. Geological 

Survey, 1973, 

361 p. 10---········· <1 8.3 22 190 <.15 <1 <7. 7 58 810 5.1 20 

1rn parts per mill ion. 
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F41 

trate, copper concentrate, and tailings from mining and milling operations in the Southeast Missouri Lead 

surficial materials of southeast Missouri 

or parts per billion (ppbl; R, sample split; ---, no data) 

Element 

K Mg Mn Mo Na Ni p Pb Sb Se Si Sr Ti v Zn Zr 

(percent) (percent) (ppm) (ppm) (percent) (ppm) (percent) (percent) (ppm) (ppm) (percent) (ppm) {ppm) (ppm) (percent) (ppm) 

Crushed ore 

0.35 8.8 700 0.030 300 0.033 > 10 <150 <0.10 1.6 70 150 7 1.2 15 

.38 7.7 1,000 .022 500 .024 >10 <150 .24 2.2 70 150 <5 1.5 <10 

Pulverized ore 

0.73 9.8 3,000 <3 0.030 70 0.067 3 <150 <0.10 2.1 70 200 5 .07 10 

• 71 9. 5 3,000 <3 .030 70 .035 2 <150 .32 2.4 70 150 <5 .07 <10 

.99 8.4 2,000 <3 .030 100 .072 5 <150 < .10 8.6 70 500 10 .2 20 

.98 8.3 3,000 <3 .030 100 .083 5 <150 < .1 0 8.8 70 300 10 .2 20 

.58 11 1,000 3 .030 300 .029 7 <150 .14 1.5 100 150 7 • 7 30 

.69 11 1,000 <3 .030 100 .025 7 <150 .22 1.5 70 150 7 • 7 <10 

.25 11 1,500 3 .022 200 .033 10 <150 <.10 .57 70 100 7 .6 15 

.23 10 1,500 3 .022 150 .038 10 <150 <.10 .53 70 70 15 • 7 <10 

.41 9.2 1,000 <3 .022 300 .052 7 <150 .14 2.2 70 100 <5 .8 <10 

.39 9.4 1,000 7 .022 500 .030 >1 0 <150 <.1 0 2.0 70 100 <5 1. <10 

.48 9.9 2,000 <3 .030 100 .026 7 <150 < .10 1.4 70 150 5 l. 15 

.48 10 2,000 <3 .015 100 <.022 10 <150 <.10 1.4 70 150 <5 .9 10 

.36 9.5 1,500 <7 .022 300 .20 >10 <150 .28 1.5 70 150 7 2.5 15 

.35 10 1,000 3 .022 200 <.022 >10 <150 <.10 1.4 70 150 7 2.6 50 

.48 9. 7 1,500 <3 .030 200 .036 7 <150 <.10 1.5 70 150 7 .7 13 

Lead concentrate 

0.090 0.25 150 5 <0.0074 2,000 0.031 >10 <150 1.8 <0.47 10 200 1.2 20 

.098 .27 150 5 <.0074 3,000 .030 >1 0 <150 1.8 < .47 10 200 1.2 20 

.13 .31 100 7 < .0074 1,000 .057 >10 <150 .93 .52 7 700 1.4 30 

.18 .• 31 150 <3 <.0074 1,500 .052 >1 0 <150 1.0 .62 10 700 1.4 20 

.14 .30 50 10 < .0074 2,000 .031 >10 <150 .26 < .47 5 200 2.2 20 

.13 .30 70 10 < .0074 2,000 .036 >1 0 <150 .52 <.47 7 200 2.1 15 

.087 .51 150 10 .0074 700 < .022 >10 <150 .27 < .47 <5 100 2. 15 

.12 .48 150 7 (.0074 700 <.022 >1 0 <150 .24 <.47 5 100 2.1 15 

.11 .48 70 10 < .0074 700 .048 >10 <150 < .10 < .47 5 150 1.3 15 

.15 .48 100 7 <.0074 1,000 <.022 >10 <150 .29 (.47 7 100 1.8 30 

.12 .55 50 10 < .0074 700 .029 >10 <150 .24 < .47 <5 150 2. 30 

.15 .52 150 20 <.0074 1 ,000 <.022 >1 0 <150 .12 <.47 5 150 2.1 20 

(.083 .24 50 10 < .0074 1,500 .041 >10 <150 .58 <.47 <5 100 1.2 20 

<.083 .25 30 10 (.0074 1 ,500 .036 >1 0 <150 .60 <.47 <5 150 1.2 20 

.12 .31 70 10 < .0074 1 ,300 .031 >10 <150 .40 < .47 5 150 1.6 20 

Zinc concentrate 

0.21 0.97 500 0.015 500 0.030 6 <150 0.52 0.63 10 500 <5 40 20 

.23 .98 300 <3 .022 700 .038 5 <150 .61 .84 15 300 7 39 20 

.16 .80 150 <3 .015 700 .026 1.5 <150 .22 (.47 10 200 <5 51 15 

.17 • 78 150 7 .015 700 .026 1.5 <150 <.10 <.47 7 150 <5 52 15 

.20 1.2 300 3 .015 700 .046 2 <150 <.18 <.60 10 150 7 48 20 

:18 1.3 300 10 .015 1,000 .030 3 <150 .13 .64 10 150 <5 48 30 

.084 .44 100 7 .015 700 <.022 5 <150 <.10 .61 5 50 <5 52 10 

.11 .59 150 5 .0074 700 .024 10 <150 (.10 .67 5 70 <5 54 10 

<.083 .36 150 5 .0074 700 .22 2 <150 < .10 < .47 <5 70 <5 53 <10 

<.083 .36 100 7 .0074 500 .024 3 <150 <.10 < .4 7 <5 100 <5 58 <10 

.084 .53 100 3 .015 300 .033 2 <150 < .10 .49 7 50 <5 56 15 

.091 .71 150 <3 .015 300 <.022 1.5 <150 .24 <.47 7 70 <5 53 15 

.14 .69 150 5 .015 700 .028 3 <150 .11 .51 7 130 <5 52 15 

Copper concentrate 

<0.083 0.090 50 0.0074 20,000 <O .022 7 <150 2.1 <0.47 <5 10 15 0.9 70 

<.083 .084 50 .0074 30,000 .21 >1 0 150 2.1 < .4 7 <5 50 7 l. 70 

<.083 .11 30 <.0074 5,000 • 17 10 <150 .35 <.47 <5 70 7 .6 15 

(.083 .11 30 <. 0074 5,000 .20 7 150 • 56 < .4 7 <5 70 5 .6 <10 

<.083 .11 15 <.0074 20,000 .19 7 300 .50 <.47 <5 70 5 .5 20 

<.083 .11 15 <.0074 20,000 .20 5 200 .59 <.47 <5 70 5 .5 <10 

(.083 .24 70 .0074 10,000 .15 7 300 .87 < .47 <5 30 15 1.4 30 

<.083 .25 50 <.0074 10,000 .13 <10 200 • 78 <.47 <5 70 5 1.6 20 

.094 .12 30 <7 < .0074 10,000 • 17 7 300 <.10 < .47 <5 30 15 • 7 30 

<.083 .11 15 (.0074 10,000 .029 7 300 .10 <.47 <5 50 7 .6 15 

<.083 .11 30 < .0074 10,000 .17 7 200 .57 <.47 <5 60 7 • 7 20 

Mill tailings 

0.53 10 1,000 3 0.022 150 O.a32 0.5 <150 0.27 2.1 70 150 7 0.2 10 

.48 10 1,000 <3 .030 200 .046 .05 <150 .24 2.1 100 100 <5 .2 <10 

Typical concentrations in surficial materials in southeast Missouri 

1.4 0.23 1,100 0.33 14 0.048 281 0.22 36 89 3,300 63 541 300 

.86 .11 660 <3 .19 8.8 .030 181 .27 41 42 3,300 37 301 260 

1.0 .so 120 .039 24 .021 451 .23 27 40 1,400 110 nol 61 
F42 GEOCHEMICAL SURVEY OF MISSOURI 

counts for more than half of this combined variation in 

five elements (arsenic, boron, iron, mercury, and zinc) 

and most of the combined variation reflects within-bed 

variability. The combined variance represents the imprecision which would be encountered in representing 

a coal bed by a single sample if that sample were 

analyzed by the methods in table 4. 

LEAD-ZINC-COPPER ORE 

The lead-zinc-copper sulfide deposits occur as 

replacement orebodies predominantly in the Bonneterre Formation of Cambrian age (Kiilsgaard and 

others, 1967, p. 45-4 7). The Southeast Missouri Lead 

District is one of the few mining districts in the United 

States that has produced over one and a half billion 

dollars worth of ore (Wharton and others, 1969, p. 63). 

Most of the past production of the district was from 

the Old Lead Belt. The New Lead Belt, or the Viburnum Trend (fig. 5), which was discovered in 1955, accounted for 85 percent of the total U.S. lead production 

in 197 4, as well as for the production of significant 

amounts of zinc, copper, silver, and cadmium 

(Vineyard, 1977). Kiilsgaard and others (1967, 

p. 45-55) presented a succinct summary of the geology 

and origin of the southeast Missouri lead deposits. 

More recently, the May 1977 issue of Economic 

Geology (v. 72, no. 3) was devoted exclusively to 

papers on the Viburnum Trend. 

Samples in this study include one sample of crushed 

ore (consisting of pieces approximately 2.5 em in 

diameter), seven of pulverized ore, seven of lead concentrate, six of zinc concentrate, five of copper concentrate, and one of mill tailings. All samples were split, 

and the resulting 54 samples were analyzed in a randomized sequence. The analytical results are given in 

table 23. Differences among the various materials may 

be judged by comparing median concentrations. (The 

median is the value of the middle item, or the average 

of the middle two items, if the items are arranged in 

order of concentration.) The median estimates the 

typical or most common concentration. Differences 

among individual samples of ore (or ore concentrate) 

may be judged by comparing averages of the replicated analyses, and the degree of analytical error is indicated by differences between the replicated analyses. 

Processing of ore to concentrate tends to increase 

levels of silver, arsenic, cobalt, nickel, and mercury 

(table 23). Antimony, chromium, selenium, and 

titanium also appear to be enriched in lead concentrate; and cadmium, molybdenum, gallium, indium, 

and selenium appear to be enriched in copper concentrate. A comparison of trace-metal levels in the different concentrates indicates that the zinc concentrate 

has the highest levels of cadmium, fluorine, gallium, 

and silver, and that the copper concentrate has the 

highest levels of arsenic, chromium, cobalt, germanium, indium, nickel, and phosphorus. Cadmium 

and silver are recovered from the concentrates during 

smelting (Kiilsgaard, 1967, p. 72; Guild, 1967, p. 73). 

Of greater environmental interest here, though, is a 

comparison of these materials to the ordinary surficial 

materials of the local landscape. Elemental concentrations most likely to be encountered in cultivated soil, 

uncultivated soil, and carbonate residuum in this part 

of southeastern Missouri are given at the bottom of 

table 23. Concentrations in cultivated soil are given as 

medians of the average concentrations measured in 

Iron, Reynolds, St. Francois, and Washington Counties (Tidball, 197 4); concentrations in uncultivated 

soils are taken from Erdman and others (1976a, table 

6); and concentrations in residuum are medians of 

average concentrations listed for residuum overlying 

the Bonneterre Formation and Eminence, Potosi, and 

Gasconade Dolomites of southeastern Missouri (U.S. 

Geological Survey, 1973, p. 10). 

The ores and concentrates are much higher than the 

surficial materials in the ore-related trace metals 

arsenic, cobalt, and nickel, and much lower than the 

surficial materials in the clay-related elements 

aluminum, barium, fluorine, potassium, titanium, 

vanadium, and zirconium. When compared to the surficial materials, the one sample of mill tailings is also 

distinctly high in arsenic, cobalt, and nickel as well as 

silver, cadmium, and the ore metals lead, zinc, and copper. The mill sample is low in aluminum, barium, 

chromium, gallium, silicon, titanium, vanadium, and 

zirconium. 

The introduction of these or similar materials into 

the near-surface environment will produce marked effects in the landscape simply because of the strong 

geochemical contrasts between ore and surficial 

materials. More important, in an environmental context, is the potential for rapid and widespread dispersal of the elements in these materials into the local 

environment. For example, Proctor, Butz, and Sinha 

(1976) noted increased concentrations of copper, lead, 

zinc, and cadmium (but not nickel) in stream sediments 

draining the Viburnum region to the north since the 

start of mining there. A general study of the chemical 

impact of the New Lead Belt on the surrounding area 

is given in Boggess and Wixson (1978). A similar impact of the Old Lead Belt is even more marked, as 

witnessed by roadside accumulations of lead in cedar 

within the belt of as much as 70 times background 

(Connor and others 1971) and by alluvial soils in Big 

Creek draining the belt which contain about 100 times 

the expected amount of lead for such soils (U.S. 

Geological Survey, 1973, table 5). 
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F43 

DISCUSSION 

Geochemical variation in the bedrock units of the 

study area is dominated by the distribution of the major rock-forming minerals: calcite, dolomite, quartz, 

and clay. this distribution tends to manifest itself at 

very large or very small geographic scales. At the 

larger scales, rocks in the eastern and southern parts of 

the study area (Sauk, Tippecanoe and Kaskaskia sequences) are rich in calcite and dolomite; they contrast 

markedly with rocks in the northern and western parts 

(Pennsylvanian System) which are rich in quartz and 

clay. At the smaller scales (representing distances of a 

few kilometers or less), this variation arisis as a result 

of interstratification of mineralogically dissimilar 

beds. 

The largest scale of variation is evident in the differences among the means of the major geologic units, 

given in tables 10-13, 16, and 21. In general, the 

statistical data for the most widespread lithic type in 

each geologic unit are given in the left-most column of 

each table, and subordinate lithic types are summarized in columns to the right. The tabled summaries 

may be used in conjunction with conventional geologic 

maps to make first-order approximations showing the 

gross regional distributions of the elements over the 

study area. Unfortunately, geologic maps in the area of 

this report do not generally show detailed distributions of the different lithic types (see Gentile, 1976, for 

example); thus, the local interstratification of contrasting lithic types, which largely controls local 

geochemical patterns (particularly in the Pennsylvanian), cannot be shown over the area as a whole. 

Bar graphs for 19 trace elements are shown in figure 

14. The graphs compare the ranges in element concentration in bedrock units of the study area. The Pennsylvanian rocks have been subdivided into two parts 

where appropriate to represent the few geochemical 

differences noted between the northern and southern 

outcrops of Pennsylvanian age. Similarly, the Precambrian rocks have been subdivided into granite and 

rhyolite on the graphs of beryllium and zirconium. 

In the graphs of figure 14, the expected concentration and the expected 68 and 95 percent ranges in concentration are shown for those units for which data in 

tables 10-13 and 21 permit computation. For many 

units, when the data are judged to be insufficient for 

such computation, only the observed range in concentration is given. The observed ranges given in figure 14 

are probably more comparable to a 68 percent expected 

range than to a 95 percent expected range because 

they are based on relatively few samples. The graphs 

indicate just how variable the chemistry of rocks in 

outcrop of the study area are. Commonly, the total 

range in concentration over all units exceeds a 

thousandfold, and for some elements (fluorine, for 

example), it exceeds ten-thousandfold. For most 

elements, the overlap of ranges tends to be large. 

The purpose of these graphs is to aid the user in 

judging the ranges of element concentration to be expected in the various types of bedrock in different 

parts of the area. Thus, a sample of bedrock from any 

part of the study area may be judged as ordinary or 

unusual by comparing its composition with the ranges 

given for the appropriate lithic type in the appropriate 

part of the area. Use of the bar graphs requires that the 

sample or samples being judg2d be assigned to the correct geologic unit, as the units have been classified for 

this study. To this end, the user may need geological 

maps or geological advice, both available from the appropriate State geological survey, State university, or 

local office of the U.S. Geological Survey. 

In examining a local field area of interest, the user 

first determines what major rock unit (or units) may be 

present. In localities far from the major geologic boundaries, the major unit underlying the area of interest 

can be determined from figure 2 or the appropriate 

State geologic map. Localities near to or straddling 

major boundaries may require detailed maps or 

geological consultation in order to determine which of 

the major units the bedrock belongs to. In particular, 

the Roubidoux-Sauk and Sauk-Kaskaskia contacts 

may prove difficult to locate in the field, especially for 

the inexperienced eye. All geologic boundaries display 

a more intricate pattern than that shown in figure 2. 

The Precambrian-Sauk contact in southeast Missouri 

is especially intricate, but because it consists of a 

carbonate-granite contrast, field examination should 

readily determine which unit is which in the field. 

Once the major unit(s) in a locality is determined, the 

lithic type(s) needs to be identified. Some types are 

readily distinguished, such as coal or carbonate rock. 

Field differentiation between limestone and dolomite 

can be difficult, as can differentiation between granite 

and rhyolite. Differentiation between fine-grained, 

laminated sandstone and silty shale may be difficult in 

the Pennsylvanian rocks. Geologic maps are generally 

of only moderate help in differentiating rock types; 

commonly, rocks are classified on maps more by 

geologic time than by chemical composition or 

lithology. If necessary, aid should be requested from 

geologists familiar with the area of interest. 

After the major rock unit and the rock type are identified, the expected ranges in composition of the rock 

types present can be read from figure 14. Also, if rock 

samples are collected and analyzed, the results can be 

compared against the graphs of figure 14 (or the summaries in tables 10-13, 16, and 21) to determine 

whether the samples in question are geochemically 

unusual. For example, copper, lead, and zinc in 14 
EXPLANATION 

Map unit Lithology 

Pennsylvanian rocks SHALE 

Sandstone 

Limestone 

Coal (Missouri) 

Dolomite (Oklahoma) 

Kaskaskia sequence LIMESTONE 

Dolomite (Missouri) 

Shale, except Chattanooga Shale 

Chattanooga Shale (Oklahoma) 

Chert 

Sandstone 

Tippecanoe sequence LIMESTONE 

Dolomite 

Shale 

St. Peter Sandstone (Missouri) 

Sauk sequence DOLOMITE 

Sandstone, Roubidoux Formation 

Sandstone, except Roubidoux Formation 

Davis Shale (Missouri) 

Precambrian rocks Granite, rhyolite 

0 Geometric mean 

-----i 

68 percent expected range 

95 percent expected range 

Observed range-Undetermined 

where dashed 

__, All data below limit of analytical 

determination-Right end of symbol 

plotted at limit 

0.5 1 2 5 1 0 20 50 

LITHIUM IN PPM (PARTS PER MILLION) MANGANESE IN PPM 

FIGURE 14.-Graphs showing trace-element concentrations in lithic bedrock units in Missouri and parts of adjacent States. 

"'%j 

~ 

~ 

0 

t::rj 

0 

CJ 

::t: 

t::rj 

~ 

-

CJ 

> t""' 

en 

Cj 

~ 

< t::rj 

~ 

0 

~ 

~ 

-

en 

en 

0 

Cj 

~ 
EXPLANATION 

Map unit 

Pennsylvanian rocks 

Kaskaskia sequence 

Lithology 

SHALE 

Sandstone 

Limestone 

Coal (Missouri) 

Dolomite (Oklahoma) 

LIMESTONE 

Dolomite (Missouri) 

Shale, except Chattanooga Shalel 

Chattanooga Shale (Oklahoma) 

Chert 

Sandstone 

Tippecanoe sequence LIMESTONE 

Dolomite 

Shale 

St. Peter Sandstone (Missouri) 

Sauk sequence DOLOMITE 

Sandstone, Roubidoux Formation 

Sandstone, except Roubidoux Formation 

Davis Shale (Missouri) 

Precambrian rocks Granite, rhyolite 

!Individual formations vary greatly. 

See table 16 

0 Geometric mean 

68 percent expected range 

95 percent expected range 

------1 Observed range-Undetermined 

where dashed 

-+---1 All data below limit of analytical 

determination-Right end of symbol 

plotted at limit 

FIGURE 14.-Trace-element concentrations-Continued 

tl:l 

tr::l 

t::l 

~ 

0 

(":) 

~ 

c::: 

z -

>-3 

en 

z 

~ 

00 

en 

0 

c::: 

~ -

> z 

t::l 

~ 

~ en 

0 

"'%j 

> t::l 

<:...; 

> (":) 

tr::l 

z 

>-3 

en 

>-3 

> >-3 

tr::l 

en 

'":r:j 

.,j::o.. 

01 
EXPLANATION 

Map unit Lithology 

Pennsylvanian rocks SHALE 

Sandstone 

Limestone 

Coal (Missouri) 

Dolomite (Oklahoma) 

Kaskaskia sequence LIMESTONE 

Dolomite (Missouri) 

Shale, except Chattanooga Shale 

Chattanooga Shale (Oklahoma) 

Chert 

Sandstone 

Tippecanoe sequence LIMESTONE 

Dolomite 

Shale 

St. Peter Sandstone (Missouri) 

Sauk sequence DOLOMITE 

Sandstone, Roubidoux Formation 

Sandstone, except Roubidoux 

Formation 

Davis Shale (Missouri) 

Precambrian rocks Granite, rhyolite 

0 Geometric mean 

68 percent expected range 

95 percent expected range 

----1 Observed range-Undetermined 

where dashed 

~ All data below limit of analytical 

determination-Right end of symbol 

plotted at limit 

t 

f 

FIGURE 14.-Trace-element concentrations-Continued 

"'%j 

~ 

m 

0 

t%j 

0 

Cl 

::c: 

t%j 

~ ~ 

Cl 

> 

~ 

00 

c::: 

~ t%j 

-<: 

0 

'"%j 

~ ~ 

00 

00 

0 

c::: 

~ ~ 
EXPLANATION 

Map unit 

Pennsylvanian rocks 

Kaskaskia sequence 

Tippecanoe sequence 

Sauk sequence 

Lithology 

SHALE 

Sandstone 

Limestone 

Coal (Missouri) 

Dolomite (Oklahoma) 

LIMESTONE 

Dolomite (Missouri) 

Shale, except Chattanooga Shale 

Chattanooga Shale (Oklahoma) 

Chert 

Sandstone 

LIMESTONE 

Dolomite 

Shale 

St. Peter Sandstone (Missouri) 

DOLOMITE 

Sandstone, Roubidoux Formation 

Sandstone, except Roubidoux Formation 

Davis Shale (Missouri) 

Precambrian rocks Granite, rhyolite 

0 Geometric mean 

68 percent expected range 

95 percent expected range 

----t Observed range-Undetermined 

where dashed 

--1 All data below limit of analytical 

determination-Right end of symbol 

plotted at limit 

2 5 10 20 50 100 

YTTRIUM IN PPM 

FIGURE 14.-Trace-element concentrations-Continued 

2 20 

ZINC IN PPM 

txl 

trj 

t::l 

~ 

0 

0 

~ 

c 

z -t-3 

C/J 

z 

~ 

C/J 

C/J -

0 

c 

~ -

> z 

t::l 

~ 

> 

~ C/J 

0 

"'%j 

> t::l 

1:.-t 

> 0 

trj 

z 

t-3 

~ trj 

C/J 

"'%j 

~ 

-.:] 
EXPLANATION 

Map unit 

Pennsylvanian rocks 

Kaskaskia sequence 

Lithology 

SHALE 

Sandstone 

Limestone 

Coal (Missouri) 

Dolomite (Oklahoma) 

LIMESTONE 

Dolomite (Missouri) 

Shale, except Chattanooga Shale 

Chattanooga Shale (Oklahoma) 

Chert 

Sandstone 

Tippecanoe sequence LIMESTONE 

Dolomite 

Shale 

St. Peter Sandstone (Missouri) 

Sauk sequence DOLOMITE 

Sandstone, Roubidoux Formation 

Sandstone, except Roubidoux Formation 

Davis Shale (Missouri) 

Precambrian rocks Granite, rhyolite 

0 Geometric mean 

68 percent expected range 

95 percent expected range 

-----i Observed range-Undetermined 

where dashed 

____, All data below limit of analytical 

determination-Right end of symbol 

plotted at limit 

0.05 0.1 0.2 0.5 1 2 5 10 20 

COPPER IN PPM 

FIGURE 14.-Trace-element concentrations-Continued 

50 100 1 2 10 20 50 100 200 500 

LEAD IN PPM 

lo%j 

~ 

00 

Q 

trl 

0 

n 

::c: 

trl 

~ 

cs 

> t"" 

r:n 

c::: 

~ 

< trl 

>-<: 

0 

'Tj 

~ 

00 

r:n 

0 

c::: 

~ 

-
EXPLANATION 

Map unit Lithology 

Pennsylvanian rocks SHALE 

Sandstone 

Limestone 

Coal ~Missouri) 

Dolomite ~Oklahoma) 

Kaskaskia sequence LIMESTONE 

Dolomite ~Missouri) 

Shale, except Chattanooga Shale 

Chattanooga Shale ~Oklahoma) 

Chert 

Sandstone 

Tippecanoe sequence LIMESTONE 

Dolomite 

Shale 

St. Peter Sandstone ~Missouri) 

DOLOMITE 

Sauk sequence Sandstone, Roubidoux Formation 

Sandstone, except Roubidoux Formation 

Davis Shale ~Missouri) 

Precambrian rocks Granite, rhyolite 

0 Geometric mean 

68 percent expected range 

95 percent expected range 

-----i Observed range-Undetermined 

where dashed 

--1 All data below limit of analytical 

determination-Right end of symbol 

plotted at limit 

0.05 0.1 0.5 10 

ARSENIC IN PPM 

FIGURE 14.-Trace-element concentrations-Continued 

50 100 10 50 100 500 

BORON IN PPM 

ttl 

tr1 

tJ 

:;:c 

0 

(j 

~ 

e 

z 

-t-3 

00 

z 

a= 

-

00 

00 

0 

e 

:;:c 

-

> z 

tJ 

~ 

> :;:c 

t-3 

00 

0 

'"%j 

> E 

> (j 

tr1 

z 

t-3 

00 

t-3 

> t-3 

tr1 

00 

~ 

~ 

c.o 
Map unit 

Pennsylvanian rocks 

Kaskaskia sequence 

EXPLANATION 

Lithology 

SHALE 

Sandstone 

Limestone (Missouri, Kansas) 

Limestone (Oklahoma) 

Coal (Missouri) 

Dolomite (Oklahoma) 

LIMESTONE 

Dolomite (Missouri) 

Shale, except Chattanooga Shalel 

Chattanooga Shale (Oklahoma) 

Chert 

Sandstone 

Tippecanoe sequence LIMESTONE 

Dolomite 

Shale 

St. Peter Sandstone (Missouri) 

Sauk sequence DOLOMITE 

Sandstone, Roubidoux Formation 

Sandstone, except Roubidoux Formation 

Davis Shale (Missouri) 

Precambrian rocks Granite, rhyolite 

llndividual formations vary greatly. 

See table 16 

0 Geometric mean 

68 percent expected range 

95 percent expected range 

-----l Observed range-Undetermined 

where dashed 

-----1 All data below limit of analytical 

determination-Right end of symbol 

plotted at limit 

10 20 50 100 200 500 1000 2000 0.05 0.1 0.2 

PHOSPHORUS IN PPM 

FIGURE 14.-Trace-element concentrations-Continued 

0.5 2 5 10 20 50 100 200 500 

CHROMIUM IN PPM 

~ 

<:n 

0 

0 

t:r1 

0 

(j 

::r: 

t:r1 

~ 

(j 

-

> 

~ 

rn 

c::: 

~ 

<: 

t:r1 

~ 

0 

~ 

~ 

00 

rn 

0 

c::: 

~ 

-
Map unit 

Pennsylvanian rocks 

Kaskaskia sequence 

EXPLANATION 

Lithology 

SHALE 

Sandstone ~Missouri, Kansas) 

Sandstone !Oklahoma) 

Limestone 

Coal ~Missouri) 

Dolomite ~Oklahoma) 

LIMESTONE 

Dolomite ~Missouri) 

Shale, except Chattanooga Shale 

Chattanooga Shale ~Oklahoma) 

Chert 

Sandstone 

Tippecanoe sequence LIMESTONE 

Dolomite 

Shale 

St. Peter Sandstone ~Missouri) 

Sauk sequence DOLOMITE 

Sandstone, Roubidoux Formation 

Sandstone, except Roubidoux Formation 

Davis Shale ~Missouri) 

Precambrian rocks Granite, rhyolite 

0 Geometric mean 

68 percent expected range 

95 percent expected range 

----1 Observed range-Undetermined 

where dashed 

~ All data below limit of analytical 

determination-Right end of symbol 

plotted at limit 

0.1 0.2 0.5 10 20 50 100 

BARIUM IN PPM 

FIGURE 14.-Trace-element concentrations-Continued 

200 500 1000 5000 0.5 2 5 10 20 

COBALT IN PPM 

50 

tc 

t;rj 

t:l 

~ 

0 

0 

~ 

c::: 

z 

-~ 

00 

z 

~ 

-

00 

00 

0 

c::: 

~ 

-

> z 

t:l 

., 

> 

~ 00 

0 

1-rj 

> t:l 

C-t 

> 0 

t;rj 

z 

~ 

00 

~ 

> 

~ 

t;rj 

00 

"'%j 

01 

........ 
EXPLANATION 

Lithology 

Map unit SHALE 

Pennsylvanian rocks Sandstone (Missouri, Kansas) 

Sandstone (Oklahoma) 

Limestone 

Coal (Missouri) 

Dolomite (Oklahoma) 

Kaskaskia sequence LIMESTONE 

Dolomite (Missouri) 

Shale, except Chattanooga Shale 

Chattanooga Shale (Oklahoma) 

Chert 

Sandstone 

Tippecanoe sequence LIMESTONE 

Dolomite 

Shale 

St. Peter Sandstone (Missouri) 

Sauk sequence DOLOMITE 

Sandstone, Roubidoux Formation 

Sandstone, except Roubidoux Formation 

Davis Shale (Missouri) 

Precambrian rocks Granite, rhyolite 

0 Geometric mean 

68 percent expected range 

95 percent expected range 

-----l Observed range-Undetermined 

where dashed 

__, All data below limit of analytical 

determination-Right end of symbol 

plotted at limit 

~ 

Ol 

t-.:l 

Q 

tz:j 

0 

CJ 

::X:: 

tz:j 

~ 

cs 

> 

~ 

r::n 

c::: 

~ 

< tz:j 

to<! 

0 

"%j 

~ 

-r::n 

r::n 

0 

c::: 

~ 

-

5 10 20 50 100 200 5 10 20 50 1 00 200 500 1 000 2000 5000 1 0,000 

NICKEL IN PPM FLUORINE IN PPM 

FIGURE 14.-Trace-element concentrations-Continued 
BEDROCK UNITS IN MISSOURI AND PARTS OF ADJACENT STATES F53 

samples of bedrock from a roadcut northeast of Centerville, Mo. (fig. 15), are listed below: 

Sample No. Rock type Element (parts per million) 

Lead Zinc Copper 

D142203 Rhyolite(?) ..... 30 105 3 

D142214 Dolomite ....... <10 11 <1 

D142217 do .......... <10 10 <1 

D142220 do .......... <10 <10 <1 

D142221 do .......... <10 14 1 

D142223 do .......... <10 <10 2 

D142224 do .......... <10 <10 <1 

D142227 do .......... <10 <10 <1 

D142228 do .......... <10 13 1 

D142229 do .......... <10 <10 <1 

D142230 do .......... <10 <10 2 

D142232 do ..... ot •••• <10 <10 2 

D142234 do .......... <10 11 3 

D142236 do .......... 15 10 200 

These samples were collected in 1969 during an investigation of an unusual field geochemical feature. A 

cedar tree (Juniperus uirginiana L.) growing on the 

roadside in this locality was found to contain 20,000 

ppm lead, 1,080 ppm zinc, and 300 ppm copper in ash 

(Connor and others, 1971). As these concentrations 

contrast greatly with typical concentrations in cedar 

ash (280 ppm lead, 380 ppm zinc, and 68 ppm copper), 

the roadside geochemical environment must be viewed 

as highly anomalous. This locality lies well within the 

Southeast Missouri Lead district, and the bedrock 

cropping out along the roadside, in which the cedar is 

rooted, was sampled to determine· if the cedar 

10 20 30 40 KILOMETERS I I I I I 

FIGURE 15.-Map showing location of cedar tree (X) with unusually 

high concentrations of lead, zinc, and copper. Major areas of 

lead mineralization are patterned. (From Connor, Shacklette, 

and Erdman, 1971.) 

chemistry was reflecting in some way an unusual 

bedrock geochemistry. 

Field examination showed the bedrock outcrop to be 

mostly dolomite, and the general location requires that 

it belong to the Sauk sequence. There was nothing 

visibly unusual about the dolomite in outcrop, and the 

trace-element chemistry of 12 samples taken from outcrop (D142214-D142234, above) fall wholly within 

ordinary limits as defined in figure 14. These data support the conclusion that the unusual cedar chemistry is 

probably not related to bedrock geochemistry. 

Nevertheless, a small mass of geochemically unusual 

rock was found in the vicinity; a small pile of sulfidebearing aggregate had been dumped by the roadside 

about 15 m from the cedar. The pile contained two 

kinds of rock: altered, mineralized rhyolite (D142203) 

and mineralized dolomite (D142236). Assignment of 

these rock types to the major units of this report is provisional, but on the assumption that both types were 

locally derived, the rhyolite chmistry may be judged 

against the Precambrian geochemical summaries and 

the dolomite against the Sauk geochemical summaries. 

The mineralized dolomite (D142236) is distinctly high 

in copper and could be viewed as a possible source for 

the high copper in the cedar, but neither rock type constitutes a realistic source for the high lead or zinc in 

the cedar. (In fact, it was finally concluded that the 

high lead, zinc, and copper reflected contamination 

from vehicular transport of lead-bearing ore.) 

Finally, a few comments on possible future sampling 

are in order. The data generated in this study are exploratory and serve primarily as a guide to general 

ranges of geochemical variation. They are viewed as insufficient to construct a geochemical map. Sampling 

undertaken to produce a map always involves a judgment as to the number of samples and the sample 

spacing needed to insure adequate stability and resolution in the resulting pattern, and such judgments can 

only be based on a knowledge of the most important 

scales at which the natural variation occurs. Estimates 

of the distribution of the total geochemical variance 

among various ranges of scale in each of the major rock 

units have been given in tables 6-9, 14, 15, 17-20, 

and 22. These estimates are expected to be of use in 

planning efficient sampling programs for more detailed geochemical investigations by future workers. 

However, the major conclusion from the present study 

is that large-scale geochemical variability within any 

specific rock type in most of the geologic units is 

generally small (compared to other scales of variation), 

and the most useful information conveyed by the 

variance estimates is that sampling to define 

geochemical variation at large scales within units 

generally will not be fruitful. In fact, variation ob-
F54 GEOCHEMICAL SURVEY OF MISSOURI 

served at such scales is likely to be spurious, the result 

of high local variation and inadequate sampling. The 

major part of the total geochemical variability in the 

bedrock of Missouri occurs between rock types of 

geologic units, and the most efficient way to predict 

the geochemical character of the bedrock in any given 

locality is to use the geochemical summaries in tables 

10-13, 16, 21, and 23 in conjunction with geologic 

maps and lithologic descriptions of the map units. 

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<l' U.S. GOVERNMENT PRINTING OFFICE, 1980-677-129/40 
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