Geochemical Anomalies of a Claypit Area, 

Callaway County, Missouri, and 

Related Metabolic Imbalance 

in Beef Cattle

GEOLOGICAL SURVEY PROFESSIONAL PAPER 807

Geochemical Anomalies of a Claypit Area, 

Callaway County, Missouri, and 

Related Metabolic Imbalance 

in Beef Cattle

By RICHARD J. EBENS, JAMES A. ERDMAN, G. L. FEDER, 

ARTHUR A. CASE, and LLOYD A. SELBY

GEOLOGICAL SURVEY PROFESSIONAL PAPER 807

A study of the concentrations of chemical elements 

and compounds in samples of clays, soils, "waters, 

and plants, and an interference syndrome in 

cattle, where mining activities have altered 

the natural geochemical environment

UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1973
UNITED STATES DEPARTMENT OF THE INTERIOR 

ROGERS C. B. MORTON, Secretary

GEOLOGICAL SURVEY 

V. E. McKelvey, Director

Library of Congress catalog-card No. 73-600086

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

Washington, D.C. 20402 Price 65c domestic postpaid or 45c GPO Bookstore

Stock Number 2401-00337
CONTENTS

Page

Abstract ........................................................................................ 1

Introduction ................................................................................ 1

Methods of sampling and analysis .......................................... 2

Sampling media and techniques ...................................... 2

Surficial deposits ........................................................ 3

Efflorescent salts ........................................................ 3

Plants ............................................................................ 4

Water ............................................................................ 4

Beef cattle .................................................................... 4

Analytical methods ............................................................ 5

Surficial deposits ........................................................ 5

Efflorescent salts ........................................................ 5

Plants ............................................................................ 5

Water ............................................................................ 6

Page

Methods of sampling and anlysis Continued 

Analytical methods Continued

Beef cattle .................................................................... 6

Results and discussion ................................................................ 6

Establishing typical geochemical values for 

sampling media as bases for defining 

anomalous values .......................................................... 6

Surficial deposits ................................................................ 7

Efflorescent salts ................................................................ 8

Plants .................................................................................... 9

Water .................................................................................... 14

Beef cattle ............................................................................ 17

Summary and conclusions ........................................................ 20

References cited ............................................. .. ........... ....... 23

ILLUSTRATIONS

Page

FIGURE 1. Map of claypit area showing sample localities ...................................................................................................................... 2

2. Aerial photograph of claypit area .................................................................................................... ....... ....... . .... 3

3. Diagram showing movement of elements through the geochemical system .................................................................... 22

TABLES

Page

TABLE 1. Approximate lower limits of detection for surficial deposits and plant materials .......................................................... 5

2. Compounds and elements in samples of surficial deposits and efflorescent salts from the claypit area .................... 8

3. Ash yield and elemental composition of plant samples from the claypit area ................................................ .... ... 12

4. Physical properties and chemical composition of surface water samples from the claypit study area ...................... 15

5. Breeding and calving history of three distinct beef cattle herds on Ranch A for the 1970 and 1971 breeding

and calving seasons .............................................................................................................................................................. 15

6. Selected trace elements in whole blood samples from beef cattle having interference syndrome and from

those that were unaffected ..................................... .....-.......... .. ... . ... .. ................................................. 15

7. Concentrations of biochemic constituents in blood serum from beef cattle having interference syndrome

and from those that were unaffected ............................................................................................................................. 16

8. Mean chemical compositions, with central 95-percent range, of media that are comparable to those sampled

in the claypit area ................................................................................................................................................................ 16

9. Concentrations of selected elements and compounds in anomalous amounts in one or more samples of clay

from the claypit area, the average of these elements and compounds in soils in the vicinity of the claypit,

and the average for the Oak-Hickory Forest soil..................................... .................................................................... 19

10. Elements and compounds that occur in anomalous concentrations in one or more samples of materials

from the claypit area .......................................................................................................................................................... 21

III

GEOCHEMICAL ANOMALIES OF A CLAYPIT AREA,

CALLAWAY COUNTY, MISSOURI, AND RELATED METABOLIC

IMBALANCE IN BEEF CATTLE

By RICHARD J. EBENS, JAMES A. ERDMAN, G. L. FEDER, 

ARTHUR A. CASE, and LLOYD A. SELBY

ABSTRACT

Geochemical studies of waters, alluvial deposits, and vegetation revealed that aluminum, beryllium, cobalt, copper, molybdenum, and nickel occurred in anomalously high concentrations 

in an area adjacent to a claypit in Callaway, County, Mo. The 

principal sources of these and other elements that were found 

in anomalous amounts are believed to be the clay, shale, limestone, coal, and pyrite that were exposed when the clay was 

mined. These geologic materials, although they contain normal 

concentrations of elements, constitute an unusually rich source 

(compared to typical soils) of certain elements for the plants 

and waters of the area. Pyrite, especially, affects the mobility 

of some of these elements because, by weathering, it produces 

sulf uric acid which increases the solubility of certain compounds.

On the two ranches studied, young beef cattle exposed to 

anomalous element concentrations in the flood plain below the 

claypile experienced a severe interference syndrome due to an 

imbalance of minerals or other nutrients in their feed or water, 

or both. The disturbance in metabolism of cattle grazing on 

the pastures effected by the claypile was most similar to chronic 

molybdenosis. Imbalance of copper and molybdenum, in addition to those of sulfate, cobalt, and other substances, may have 

contributed to this syndrome.

Anomalous concentrations of elements may exist at many 

other locations in Missouri and throughout the Midwest where 

similar materials are brought to the surface by clay and coal 

strip-mine operations (especially if pyrite is present).

INTRODUCTION

Claypits, with associated mounds of clay and debris 

distributed about the ground surface, are anomalous 

features compared to naturally occurring surficial materials. If such materials are suspected of contributing 

unusual amounts of certain elements to the surroundings, the desirability of making detailed studies of their 

chemical nature is apparent. One such situation in Caliaway County, reported to the Environmental Health 

Surveillance Center, University of Missouri, was possibly contributing to breeding failures and growth suppression in beef cattle that ranged nearby. The clay 

deposit and its epidemiological implications were called 

to the attention of U.S. Geological Survey personnel 

who currently are engaged in a geochemical survey of

Missouri. In this report we describe the results of an 

exploratory geochemical study of the area and interpret 

the effects of the clay deposit and mining activities on 

the health of beef cattle in nearby pastures.

The purpose of this report is to call the situation to 

the attention of environmental scientists who may wish 

to compare our findings and interpretations with those 

resulting from future studies of situations that may be 

similar. Only through continuing studies of this kind 

will complete and final interpretation of the health 

effects be possible.

The western part of the claypit area (fig. 1) is characterized by a flat upland surface (generally above 800 

ft in altitude) underlain by interbedded clay, shale, 

sandstone, and coal of Pennsylvanian age, and largely 

overlain by a mantle of loess of undetermined thickness. The eastern part of the area (generally below 800 

ft in altitude) is moderately well dissected and is underlain by carbonate rocks of Mississippian and Ordovician 

age. An oak-hickory forest constitutes the predominant 

native vegetation in both areas. An abandoned claypit 

several hundred feet wide, about 60 feet deep, and 

partly filled with water is located at the "break" in the 

topography near the west edge of the area (fig. 2). The 

clay, which was mined for use in the ceramic industry, 

occurred in a sink that had developed in the underlying 

carbonate rock. McQueen (1943, p. 47) noted that in 

this part of Missouri, fire clay commonly is mined from 

deposits in sinks.

A large claypile and a smaller pile immediately north 

of it are located on a ridge at the east margin of the pit. 

The large pile consists of clay with abundant fragments 

of both gray shale and carbonaceous shale, and smaller 

amounts of pyritic material, gypsum, and carbonate 

rock, whereas the smaller pile consists almost exclusively of clay. Some surface runoff from the claypiles 

drains westward into the claypit; the remainder drains 

northward, eastward, and southward into Rocky Creek.
GEOCHEMICAL ANOMALIES OF A CLAYPIT AREA, MISSOURI

92° 02' 30"

1000 2000 3000 FEET 

__I

FIGURE 1. Clay pit area, Callaway County, Mo., showing locations of numbered sites where samples 

were collected. Base from U.S. Geological Survey, New Bloomfield (1969) and Osage City (1967), 

Mo., 1:24,000.

Only the cattle that were pastured on land with direct 

access to Rocky Branch were reported to have metabolic disorders.

Ebens (geologist), Erdman (botanist), and Feder 

(hydrologist) of the U.S. Geological Survey conducted 

the geochemical studies. Case (clinical veterinarian, 

toxicologist) of the School of Veterinary Medicine, 

University of Missouri Columbia, and Selby (epidemiologist, veterinarian) of the Environmental Health 

Surveillance Center and the School of Veterinary Medicine, University of Missouri Columbia, conducted the 

studies of metabolic imbalances of the beef cattle. Partial support of these studies by Selby was provided by 

U.S. Public Health Service Grant No. E. S. 00082 to 

the Environmental Health Surveillance Center.

We express our appreciation to Messrs. Z. S. Altschuler, Hansford T. Shacklette, Richard W. White, 

and Mrs. Josephine G. Boerngen, all with the U.S. 

Geological Survey, for their assistance in collecting and 

preparing samples, and in interpreting the data. We are 

also indebted to Terrence M. Curtin of the School of

Veterinary Medicine, University of Missouri Columbia, for reviewing the manuscript. Messrs. David P. 

Hutcheson (nutritionist, School of Veterinary Medicine, University of Missouri Columbia), Larry Edmonds (Enviromental Health Surveillance Center, University of Missouri Columbia), and Vincent Raaf 

(Area Livestock Extension Agent) assisted in gathering and interpreting data. We thank Messrs. Robert 

Helzer and Byran Hungate (ranchers), and Merrill 

Townley (veterinarian) for their cooperation in conducting the field studies.

METHODS OF SAMPLING AND ANALYSIS 

SAMPLING MEDIA AND TECHNIQUES

Samples were collected to determine which elements 

were present and in what concentrations in surficial 

deposits, vegetation, and water in order to characterize 

the geochemistry of the claypit area. Studies of metabolic imbalances of the beef cattle conducted at the 

ranches were supplemented by laboratory examinations 

and analyses of selected materials.
METHODS OF SAMPLING

FIGURE 2. Aerial view of claypit area, Callaway County, Mo. 

This view, looking south, shows the smaller claypile (left 

foreground) and the larger claypile (left center) with diversion ditches leading to the water-filled claypit (right center). 

Before these ditches were constructed, some runoff from both 

claypiles flowed to the left, and entered a branch of Rocky

SURFICIAL DEPOSITS

Surficial deposits, as defined in this study, consist of 

clay and rock collected from the claypiles and the claypit, alluvium collected from two forks of Rocky Branch 

that drain slopes and small valleys below the claypiles 

and claypit, and soils collected from plant-sampling 

sites and from upland fields that are not affected by 

drainage from the claypiles or pit. A total of 31 samples 

of surficial materials from 14 sites was collected. The 

locations of the sampling sites are given in figure 1.

Clay, rock, and some soil samples were collected at 

depths ranging from a few centimeters to 15 cm by 

using a mason's hammer or a trowel. The eight samples 

of loess soils were 1-inch-diameter cores obtained with 

a stainless steel punch auger from depths of 2-15 cm. 

Samples of both pyritic material and gypsum were 

handpicked from the surface of the large claypile. All 

samples were placed in waterproof paper containers, 

dried in an oven with circulating air at 50 °C, and pulBranch. Overflow from the claypit enters a branch of Rocky 

Branch to the right of the wooded area, thence down the 

valley to low areas of the livestock pasture shown in the left 

background. Dump truck at lower right indicates scale. 

Photographed February 1972.

verized in a ceramic mill to approximately minus-100- 

mesh particle size.

EFFLORESCENT SALTS

Yellowish-brown efflorescent salts a few millimeters 

thick at water seeps covered several tens of square feet 

at the southeast side of the large claypile. Two samples 

of this material were picked by hand from the ground 

surface and placed in waterproof paper containers. It 

was not possible to mechanically remove all clay particles from the efflorescent salts. Therefore, in order to 

obtain a better estimate of the elements present in each 

component of the samples, the following separation 

procedure was used: 43 g (grams) of one of the samples 

(No. 10, table 2) was placed in 1,600 ml (milliliters) of 

distilled water at about 35°C for 24 hours. This material was then filtered with a ceramic candle that had a 

maximum pore radius of 0.6 micron, thus removing 16.5 

g of insoluble residue from the 43-g sample. The insoluble residue, sample 12, table 2, was dried at 90°C and
GEOCHEMICAL ANOMALIES OF A CLAYPIT AREA, MISSOURI

pulverized in a ceramic mill to a grain size of minus-100 

mesh. The filtrate was evaporated at 25°C and the 

resulting evaporative residue, sample 11, table 2, was 

air dried and pulverized in a ceramic mill to a grain 

size of minus-100 mesh.

PLANTS

A total of 36 plant samples, divided into four suites, 

from 10 sites was collected and analyzed. The sampling 

localities are indicated by the numbered sites in figure 1.

Two samples of redcedar trees that grew either in 

native soil or in claypile material were collected on 

May 7, 1971. One of these samples occurred near the 

edge of the claypit west of the smaller claypile (fig. 1, 

site 1). The other sample was collected at site 3 where 

some dead oak trees stood in clay deposits that resulted 

from erosion and downslope movement from the larger 

pile onto the native soil.

A second suite of samples consisted of grasses and 

forbs (broad-leafed herbs) that were collected on June 

17 in conjunction with water sampling, and their localities correspond to the water sampling sites shown in 

figure 1, as follows: site 2, the south margin of the claypit pond; site 9, streamside about 1,000 feet east-southeast of the claypile; site 12, margin of a farm pond 

northeast and across the valley from the claypile; and 

site 18, streamside on Ranch B about 1.5 miles downstream from the claypit.

Woody native plant species sampled June 30 were 

the same species as those sampled in an earlier study 

which was made for the purpose of chemically characterizing the vegetation-type areas of Missouri, and for 

which we had already estimated typical concentrations 

and ranges of selected elements in the plant species. 

These samples were collected along the south fork of 

Rocky Branch along a traverse downslope from the 

claypile.

The final suite of plant samples, composed mostly of 

white sweetclover, was collected in late September. 

This plant species was believed, on the basis of an 

earlier analysis, to concentrate molybdenum; moreover, 

these plants showed evidence of having been grazed by 

cattle. Certain species of plants associated with white 

sweetclover also were found to contain anomalously 

high concentrations of molybdenum, and were, therefore, included in this suite of samples.

Plant samples were cut with pruning shears, placed 

in paper or cardboard containers, and dried in an oven 

with circulating air at 50°C. Samples of forbs that were 

used for separate analyses of roots and aboveground 

parts were pulled from the ground and thoroughly 

washed in tapwater before being dried. The 6- to 10- 

inch terminal parts of deciduous tree and shrub stems 

(branches) without leaves were used for analysis. The 

redcedar samples were similar, but included both stems

and scalelike leaves. Forbs and grasses were sampled 

by cutting the plants near the ground, and the samples 

included stems, leaves, and, if present, flowers and 

seeds. These samples were not washed.

WATER

Water samples were collected from four sites (fig. 1, 

sites 2,9,12, and 18) on June 17. The samples were not 

filtered, in order to determine the trace elements that 

were present in the water-sediment mixture that the 

cattle might drink. Sites 9 and 18 were chosen because 

adversely affected cattle had access to the water at 

these sites. Even though cattle did not have direct 

access to water in the claypit (site 2), during intense 

rainfall the claypit overflowed and drained into streams 

that flowed through the pastures. The farm pond at 

site 12 was chosen as a control because it received no 

drainage from the claypiles or claypit.

Samples were collected in acid-washed polyethylene 

bottles by immersing them 1 foot below the surface of 

the water. Each bottle was filled and drained twice with 

sample water before collecting the final sample. The 

trace-element samples were treated with 1.5 ml double 

redistilled reagent grade concentrated nitric acid. 

Samples for nitrogen-cycle determinations were collected in 500-ml bottles, treated immediately with 30 

mg mercuric chloride, and placed in an ice-filled cooler. 

The samples in which the various forms of nitrogen 

were to be determined were shipped in an ice-filled 

cooler by bus to the U.S. Geological Survey laboratory 

in Little Rock, Ark., where they were analyzed immediately in order to minimize the effects of changes in 

the nitrogen cycle components on the analyses. Field 

determinations of pH, alkalinity, specific conductance, 

the temperature were made at each sample site.

On July 16 a raw-water sample was collected for 

microscopic determination of the presence and concentrations of potentially harmful microorganisms in 

the claypit water. One liter of water was filtered 

through a 50-mm-diameter 0.45-micron filter. The final 

15 ml of unfiltered water and the filter were placed in 

a petri dish. Within 2 hours of collection, Robert Lipscomb, U.S. Geological Survey, St. Louis, Mo., prepared 

a wet slide of an aliquot of the water sample which he 

examined for the presence of microorganisms.

BEEF CATTLE

On two ranches, designated "Ranch A" and "Ranch 

B" in this report, beef cattle were pastured in fields 

adjacent to and downstream from the claypile area 

(fig. 1). Ranch A is immediately adjacent to this area, 

and cattle on this ranch were more intensively studied 

than those on Ranch B located farther downstream 

from the area. A thorough epidemiological workup of 

the cattle on Ranch A was undertaken, and cattle on
METHODS OF SAMPLING AND ANALYSIS

both ranches were examined during numerous visits.

On Ranch A, in 1970, the cattle consisted of two 

distinct herds one composed of 54 Angus cows 7 years 

old, the other, 66 Angus cows 4 years old. In 1971 an 

additional herd of 24 Charolais cows 4 years old was 

brought to the ranch. Both Angus and Charolais bulls 

serviced the herds (table 5). Only the herd of 4-yearold Angus cows showed signs of metabolic imbalance. 

On Ranch B, one yearling and four older Charolais bulls 

exhibited these signs. The yearling bull was purchased 

from a ranch in southwest Missouri in April 1970.

Our first visit to observe the cattle was in May 1971. 

Frequent visits to the ranches were made throughout 

the summer and autumn of 1971 to examine the cattle, 

to collect specimens, and to discuss the problem with 

the ranchers, the local veterinarian, and the Area Livestock Extension Agent. Blood samples of the affected 

and unaffected cattle were analyzed for selected trace 

elements, blood serum enzymes, and macrominerals, 

and the pH of rumen samples was determined. Cattle 

were isolated from the claypit area and flood plain, and 

rations were recommended to correct the interference 

syndrome.

ANALYTICAL METHODS

SURFICIAL DEPOSITS

Concentrations of elements in surficial deposits were 

determined by analysis of pulverized samples in the 

laboratories of the U.S. Geological Survey in Denver, 

Colo. and Washington, B.C. Magnesium, sodium, 

cadmium, lithium, and zinc contents were determined 

by atomic absorption methods, arsenic by colorimetric 

methods, fluorine by the fluorine selective ion electrode 

method, and mercury by the mercury detector method 

described by Vaughn (1967). Organic carbon concentrations were determined by making separate analyses 

for total carbon and carbonate carbon and computing 

the difference, according to the method described by 

Tourtelot, Huffman, and Rader (1964). Silicon, aluminum, ferrous iron, calcium, potassium, phosphorus, and 

selenium contents were determined by X-ray fluorescence methods.

Concentrations of the other elements were determined by semiquantitative spectrographic analysis. 

The spectrographic method used is virtually that 

described by Myers, Havens, and Dunton (1961), but 

the analytical results are given in six, rather than three, 

steps per order of magnitude. These results were 

reported in geometric brackets having the boundaries 

1.2, 0.83, 0.56, 0.38, 0.26, 0.18, 0.12, and so forth, percent or parts per million (ppm); the brackets are identified by their respective geometric midpoints, such as 

1.0, 0.7, 0.5, 0.3, 0.2, and 0.15. Thus, a reported value of 

0.3 ppm, for example, identifies the bracket from 0.26 

to 0.38 as the analyst's best estimate of the concentration. The precision of a reported value is approximately 

plus or minus one bracket at the 68-percent level of 

confidence, and plus or minus two brackets at the 95- 

percent level.

The approximate lower limits of analytical detection 

for surficial deposits are given in table 1. Some combinations of elements in a sample, however, affect these 

limits. Concentrations somewhat lower than these 

values may be detected in unusually favorable materials, whereas these limits may not be attained in unfavorable materials.

Surficial materials, except soils, were analyzed by 

X-ray diffraction to determine their mineral content.

EFFLORESCENT SALTS

Efflorescent salts were analyzed for element concentrations by the same methods that were used for 

samples of surficial deposits and, in addition, were 

examined by X-ray diffraction to determine which minerals were present.

PLANTS

The plant samples were oven dried, then pulverized 

in a Wiley mill. Wet digestion methods were used to 

prepare the samples for determining the arsenic, mercury, and selenium concentrations. For determining the 

concentrations of other elements in the samples, the 

pulverized plants were transferred to ceramic crucibles,

TABLE 1. Approximate lower limits of detection for surficial 

deposits and plant materials

[Analyses made by semiquantitative spectrographic method, except as indicated. Dry surficial material was used for analyses of all elements. Dry plant 

material was used for arsenic, mercury, and selenium analyses; plant ash was 

used for analyses of all other elements. Limits are given in parts per million 

., no data available]

Lower limit of 

detection (ppm)

Surficial Plant 

deposits materials

AL....................... UO.OOO 20

As....................... 3.2 3.25

B......................... 20 50

Ba....................... 1.5 3

Be....................... 1 2

C, total............... 4 500 ..........

C, in CO3........... 4 100 ..........

Ca....................... '1,000 3 150

Cd....................... 2 1 2.3

Ce........................ 150 ..........

Co....................... 3 "1

Or....................... 1 2

Cu....................... 1 2

Dy................. ..... 50 ..........

F . . 540

T e in Fe2O3....... '1,000 «20 

Ga....................... 5 5

Gd....................... 50 ..........

Hg...................... '.01 3.025

K......................... '1,000 250

La....................... 30 70

Li................... ...

Mg...................... 

Mn......................

Mo . .

Na .. .

Nb......................

Nd......................

Ni.

P.........................

Pb.......................

Pr.... ..... .... . .

Se...~ ... ...........

Sc .......... .... ......

Si........................

Sn.......................

Sr.......................

Ti.......................

V........................

Y.... .

Yb......................

Zn.......................

Zr.......................

Lower limit of 

detection (ppm)

Surficial 

deposits

25 

2300 

1 

3 

2 100 

10 

70 

5 

*300 

10 

100 

U 

5 

UO.OOO

6 

100 

2 

7 

10 

1 

10 

10

Plant 

materials

24 

50 

2 

"4 

2 100

2 

»40 

20

».6 

6

20 

10

6 

6 

20 

2 

226 

20

1 Analysis by X-ray fluorescence method. 

2 Analysis by atomic absorption method. 

3 Analysis by colorimetric method. 

4 Analysis by method of Tourtelot, Huffman, and Rader (1964). 

5 Analysis by fluorine selective ion electrode method. 

6 Fe, total. 

7 Analysis by mercury detector method.
GEOCHEMICAL ANOMALIES OF A CLAYPIT AREA, MISSOURI

weighed, and burned to ash in an electric muffle furnace 

in which the heat was increased 50°C per hour to a 

temperature of 550°C and held at this temperature 

for about 14 hours. The ash was then weighed to determine the ash yield of the dry plant sample. Colorimetric 

methods were used to analyze the ash for phosphorus 

and molybdenum (Reichen and Ward, 1951), and the 

atomic absorption method was used for cadmium, calcium, cobalt, lithium, potassium, sodium, and zinc 

determinations.

Concentrations of the remaining elements in ash 

were determined by the same semiquantitative spectrographic method described under "Surficial Deposits," 

except that the ash was diluted with an equal weight 

of matrix composed of sodium silica (10 percent Na).

The lower limits of detection of the analytical 

methods that were used for plant analyses are given in 

table 1. Several samples did not contain enough material for these lower limits to be attained; therefore, the 

detection limits were higher for elements in these 

samples.

WATER

Because of the possibility of changes occurring 

rapidly in certain chemical properties of water after 

sampling, determinations of pH, alkalinity, specific conductance, and temperature were made at the sample 

sites. Procedures for making these determinations were 

given by Brown, Skougstad, and Fishman (1970).

All laboratory determinations, except those of nitrogen cycle components, were made in the U.S. Geological 

Survey laboratories in Denver* Colo., under the supervision of Marvin W. Skougstad. The nitrogen cycle 

determinations were made in the Survey laboratories 

in Little Rock, Ark., under the supervision of Charles 

T. Bryant.

Cadmium, chromium, cobalt, lead, zinc, mercury, 

arsenic, and nitrogen cycle components were determined by methods given by Brown, Skougstad, and 

Fishman (1970). All other determinations were made 

by spectrographic methods described by Barnett and 

Mallory (1971).

BEEF CATTLE

Whole blood samples from the beef cattle studied 

were analyzed for trace-element content by the 

Environmental Trace Substances Center, Research 

Reactor Facility, Columbia, Mo., under the supervision 

of Dr. James O. Pierce. Whole blood samples were collected by venipuncture in tubes containing 6 mg EDTA 

(ethylenediamine tetraacetate) per 5 ml of blood, and 

were wet ashed with a 5:1 ratio of nitric and perchloric 

acid. The residue was then dissolved in 1-percent nitric 

acid and the sample analyzed by atomic absorption 

spectrophotometry, using recommended methods (Kerber, 1971).

Blood serum analyses, using the methods of Tumbleson (1969), were performed by Dr. David P. Hutcheson, School of Veterinary Medicine, University of 

Missouri at Columbia, for the determination of the 

biochemic constituents cholesterol, total bilirubin, 

glutamic-oxaloacetic transaminase, alkaline phosphatase, lactic dehydrogenase, total protein, creatinine, 

blood urea nitrogen, calcium, inorganic phosphorus, 

sodium, potassium, and chloride. The pH of rumen 

samples was determined by Selby and evaluated by 

Dr. Hutcheson.

RESULTS AND DISCUSSION

The results of laboratory analyses of surficial materials, efflorescent salts, plants, and water samples are 

given in tables 2-4. The data and observations pertaining to beef cattle are given in tables 5-7.

ESTABLISHING TYPICAL GEOCHEMICAL VALUES FOR

SAMPLING MEDIA AS BASES FOR DEFINING

ANOMALOUS VALUES

The substances that occur in anomalous concentrations in various surficial materials must be identified 

by evaluating the deviations of their concentrations 

from typical concentrations in comparable materials 

from other areas. Anomalous values can only be defined 

as deviations from values that are considered typical 

for the materials under consideration. Therefore, typical values must first be established for each category of 

material; then a judgment must be made as to the 

degree of deviation from the typical value that is 

required to classify other values as "anomalous." Deviations above the typical values may, for convenience, 

be designated "positive anomalies," and those below, 

"negative anomalies."

The selection of criteria that are to be used in 

distinguishing anomalous from normal concentrations 

is a matter of judgment that must be made according 

to the requirements of the study. We have chosen to 

define normal concentrations as those that are within 

the central 95-percent range of concentrations found 

in comparable materials thought not to have been 

affected by pollution; anomalous concentrations are 

those that occur outside this range.

The geometric mean is a measure of central tendency 

of the frequency distribution and, as such, is an estimate of the typical or most common concentration for 

the element or compound. Approximately 95 percent 

of the values occur in the range whose limits are the 

geometric mean divided by the square of the geometric 

deviation and the geometric mean multiplied by the 

square of the geometric deviation. The central 95- 

percent ranges of the distributions of each element and 

compound were computed on this basis (table 8), and 

these ranges were used to define anomalous concentra-
RESULTS AND DISCUSSION

tions of the chemical constituents in samples from the 

claypit area as given in table 10. If the concentration 

of an element or compound was beyond the normal 95- 

percent range in one or more samples of a given 

material (table 10), this element or compound was 

considered anomalous in that material. For example, 

the geometric mean alumina content of B-horizon soils 

from the Oak-Hickory Forest vegetation type area in 

Missouri is 5.1 percent and the geometric deviation is 

1.47 (table 8). Probably 95 percent of the samples have 

alumina contents in the range 5.1-f- (1.47) 2 (2.4 percent) to 5.1 X (1.47) 2 (11 percent). These two limits 

define the range against which the alumina analyses of 

the clay samples from the claypit area were compared; 

in this example, alumina concentrations in all five of 

the clay samples were judged to be beyond the normal 

95-percent range and are, therefore, anomalous with 

respect to the B-horizon soils.

Typical values that were used to identify anomalous 

values in sampling media from the claypit area are 

given in table 8. This table gives geometric means and 

geometric deviations for the concentrations of elements 

and compounds in different categories of surficial 

deposits and vegetation; they are believed to be the 

best available data on typical concentrations of elements in the respective materials. The data in table 8 

were developed from sampling programs that were 

entirely unrelated to the claypit study. (See Shacklette, Erdman, and Keith, 1971.) The means and deviations in this table are antilogs of the arithmetic means 

and standard deviations, respectively, of the logarithms 

of the analytical values. Where some of the element 

concentrations were determined to be less than the 

sensitivity of the analytical method (table 1), the mean 

and standard deviations of the logarithms were estimated by means of a censored-distribution technique 

devised by Cohen (1959).

No reliable data were available for use as norms for 

identifying anomalous concentrations of elements and 

compounds in water.

SURFICIAL DEPOSITS

The concentrations of selected elements in 31 

samples of surficial deposits collected from the claypit 

area are given in table 2. Sample site numbers, dates 

samples were collected, and a brief description of the 

samples are included. The mineralogy, as determined 

by X-ray diffraction analyses, is shown for all the 

samples except those of soil.

In order to ascertain the possible effect that the 

mined clay could have on the local environment, the 

elemental composition of the clay was compared with 

that of soils of the area, because both of these materials 

influence the water in Rocky Branch and the supply of

elements available to plants. The elemental compositions of clays from the claypiles and claypit differ 

markedly from those of soils in the problem area and 

from most B-horizon soils from the Oak-Hickory Forest, the vegetation type which occurs throughout much 

of southern Missouri and in which the claypit area is 

located (table 9). The elements listed in table 9 are 

those that were found to occur in anomalous concentrations in one or more samples of clay. The four samples 

of soil (Nos. 32-35, table 2) from the white sweetclover 

sampling localities were composed mostly of clay on the 

large claypile or of clay washed from the claypile, and 

their elemental composition is similar to that of the 

samples designated as clay.

Except for nickel in sample 21 (table 2), the concentrations of trace elements in a sample of dolomite (No. 

19) and in two samples of carbonate residuum (Nos. 

20 and 21, table 2) collected from the walls of the claypit are not anomalously high with respect to the soils. 

A sample of shaly coal (No. 4, table 2) collected from 

the large claypile contained concentrations of beryllium, lead, lithium, mercury, molybdenum, scandium, 

vanadium, ytterbium, and zinc that are anomalously 

high with respect to the soils, although apparently normal for this type of coal.

The elemental compositions of four samples of alluvium (Nos. 13, 14, 16, and 17, table 2) collected from 

the beds of creeks that drain away from the claypiles 

are similar to those of samples of clay from the claypiles. The clay-size fraction and the coarse-grained 

fraction of the alluvium do not differ significantly in 

trace-element composition. The amounts of clay and 

shale particles which are derived from the claypiles and 

carried by creeks, and the maximum distance that the 

particles are carried, are not known. However, clay 

similar to that found in the claypiles has coated rocks 

in Rocky Branch and occurred as deposits (as much as 

10 cm thick at sample site 5) in ephemeral pools in the 

creekbed as far downstream as Ranch B, the farthest 

downstream point in the study area. Clay and shale 

particles similar to those found in the claypiles were 

observed on parts of the flood plain several hundred feet 

downstream from sample site 6 (fig. 1), the farthest 

point downstream that the flood plain was inspected.

Gypsum (CaS04 'H2 0) was found to be widespread 

on the surface of the large claypile and probably was 

produced by the action of sulfiiric acid solution on calcium-bearing minerals in the claypile. Sample 8 (table 

2), which is composed of gypsum, clay, quartz, apatite, 

and crandallite(?), had anomalously high concentrations of dysprosium, gadolinium, phosphorus, praseodymium, samarium, and yttrium compared to those 

found in the clays and the other gypsum sample that 

were analyzed. In this sample these elements probably
8 GEOCHEMICAL ANOMALIES OF A CLAYPIT AREA, MISSOURI

occurred in the clay or in the phosphate minerals apatite and crandallite. Barium, chromium, selenium, and 

strontium were the only trace elements detectable in 

gypsum sample 7 (table 2) although the concentrations were low; other trace elements, if present, were 

in concentrations below the detection limits given in 

table 1.

Pyritic material was widely disseminated throughout 

the large claypile; the presence of pyrite was verified 

by X-ray diffraction of samples 5 and 6 (table 2). 

Sample 5 was contaminated with clay, gypsum, and 

calcite; hence, the chemical data for this sample reflect 

the chemical composition of these materials. The concentration of cobalt was high in this sample compared 

to that found in the clays. Sample 6, which was only 

slightly contaminated with clay particles, contained no 

abnormally high concentrations of trace elements compared to the composition of normal soils from the area.

[Ana

The presence of pyrite is important in geochemical systems, however, because the weathering of this material 

results in the formation of sulfuric acid, which increases 

the solubility of certain compounds. The mobilities of 

constituent elements in these compounds, therefore, are 

generally increased.

EFFLORESCENT SALTS

Chemical properties of the efflorescent salts are given 

in table 2. X-ray diffraction analyses of sample 11 

(table 2) , which consisted of residue obtained by evaporating the soluble fraction of the efflorescent salts, and 

of sample 10 (table 2) indicate that alunogen, a 

hydrous sulfate of aluminum having the formula 

Al2 (S04 )3*nH2 0, is the dominant crystalline phase of 

these salts. Palache, Berman, and Frondel (1951, p. 

538-539) reported that alunogen occurs principally as 

an efflorescence or crevice filling in coals, shales, and 

slates that contain pyrite, and that the mineral is

TABLE 2. Compounds and elements in samples of surficial

Sample L«t>ora- Site Date 

>TO tory No. sampled 

No. (fig. 1) (1971)

Compound or element

Material 

sampled Remarks SiOa 

(percent)

AhOa 

(percent)

Total Fe 

as FeaOa 

(percent)

MgO 

(percent)

Large claypile

i

2 

3 

4

5 

6 

7 

8

9

10 

11

12 

13 

14

D149910 1

D150439 1 

D150448 1 

D149912 1 

D149913 1 

D150447 I 

D150433 1 

D150450 1

D150434 1

D150435 1 

D150436 1

D150437 1 

D154026 5 

D154027 5

May 7

June 30 

......do......

May 7 

......do......

June 30 

......do......

......do......

......do......

......do......

......do......

......do...... 

Sept. 28

........ do .......................

........ do .......................

...... do .........................

...... do .........................

Efflorescent salts ..... 

...... do .........................

...... do .........................

...... do ........................

...... do .........................

do ....

... 1-5 mm temporary salt crust (mostly alunogen) 

on clay at seeps, base of large claypile

... ........ do ................................................................................

... Insoluble residue obtained from sample 10 ................

immediately below sample 13 .....................................

48 

45 

44 

13 

8 

1 

.3

35

23 

18

43 

52

52

30 

29 

31 

8 

4 

1 

.5

24

20 

17

.2 

24 

28

27

2.2 

2 

1.4 

16 

35 

65 

<.l

2.2

6.5 

6.1

~~7.Y 

3.9

2.6

0.8 

.64 

.6 

.08 

.28 

.1 

.01

.41

1.04 

1.11

.03 

.56 

.97

.71

Small claypile

15

16 

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

83

84

35

D149911

D154024 

D154025

D150446

D150446

D150442

D150449

D149914

D149915

D149916

D149917

D149918

D149919

D149920

D149921

D150440

D150441

D154028

D154029

D164030

D154031

1

10 

10

2

2

2

2

8

7

11

13

14

15

16

17

6

4

1

1

2

4

May?

Sept. 28 

......do......

June 30

......do......

......do......

......do......

May?

......do......

......do......

......do......

......do......

......do......

.... do .

......do......

June 30

......do......

Sept. 26

......do......

. do..

......do......

Clay .............................

Alluvium ...................... 

...... do ...........................

Clay ..............................

Silty dolomite ..............

Carbonate residuum....

...... do ............................

Loess soils ....................

do ............................

...... do ............................

...... do ............................

...... do ............................

. . do ............................

...... do ............................

...... do ............................

Soils ..............................

...... do ............................

do

...... do ............................

...... do ............................

do

. Kaolinite; lesser amounts of illite and

mixed-layer clay ...................................................

. Clay, upper 3-10 cm of streambed deposit......... 

. Sand, silt, and clay collected in creekbed

immediately below sample 16 .............................

Claypit

. Kaolinite; lesser amounts of illite and

mixed-layer clay ...................................................

Collected from drainage ditch,

southeast part of claypit............ ......................

. Collected from north wall of claypit...... .............

do .....................................................

Soils from vicinity of claypit

Associated with white oak and buckbrush

sampling localities ...............................................

do ...

Associated with white sweetclover

sampling localities ...............................................

do

do

do . ........... ... ..

......... 46

49

.......... 51

.......... 41

......... 5

.......... 79

.......... 71

.......... 75

.......... 76

.......... 70

.......... 70

.......... 82

75

.......... 77

.......... 82

......... 77

.......... 78

......... 47

.......... 59

......... 50

.......... 54

34

34

31

33

1

8

11

9

9

11

11

7

8

8

7

8

7

32

25

30

29

1.6

1.3

1.7

1

2

2.8

5.7

2.8

2.5

4.7

4.4

2

3.8

3

1.7

2.9

2.1

1.4

2.8

1.7

2.6

0.56

.56

.64

0.42

16

.45

.64

0.52

.48

.86

.78

.36

.47

.48

.29

.38

.33

.56

.89

.58

.90
RESULTS AND DISCUSSION

formed by the action of sulfate solutions resulting from 

the oxidation of the pyrite on aluminous minerals.

Analysis of the efflorescent salts served to identify 

some of the elements that move in solution in the immediate vicinity of the claypile. Samples 9 and 10 (table 

2) reflect, in part, the chemical composition of the clay 

from the large claypile because it was not possible to 

remove all clay particles from the salts. The chemical 

composition of the residue sample (No. 11) derived 

from the evaporated soluble material in sample 10 

reveals soluble elements in the efflorescent salts, plus 

those that were released from the clay by the acid 

solution.

Aluminum, cobalt, copper, and nickel have the highest concentrations in sample 11, and barium, beryllium, 

chromium, gallium, lithium, manganese, scandium, 

ytterbium, yttrium, and zinc are present in lower concentrations. Other trace elements analyzed for, if

deposits and efflorescent salts from the claypit area

were found in a sample, praseodymium with a lower detection limit of 1 ppm was looked for in the same sample but was not found. If yttrium 

concentration in a sample exceeded 50 ppm, the following elements, with their stated lower detection limits, were looked for in the same 

sample, but were not found: Erbium, 50; holmium, 20; lutetium, 30; terbium 300; and thulium, 20. Asterisk, analysis by a semiquantitativ« 

spectrographic method. Results are reported as geometric midpoints of geometric classes, in the series 1, 1.5, 2, 3, 5, 7, 10, 15, and so forth.

present, were in concentrations below the detection 

limits given in table 1. The complete distance that 

these elements are moved in solution or in suspended 

solids by runoff from the claypile is not known. However, the crust of efflorescent salts that was sampled on 

June 30 was not observed during a visit to the claypit 

area on September 28. A 3-inch rainfall on September 

22 is thought to have washed the efflorescent salts from 

this area, and conditions conducive to the formation of 

new crusts of salts were not in evidence.

PLANTS

Chemical analyses of the 36 plant samples from the 

claypit area are given in table 3. Where several samples 

of a species were collected and analyzed, the samples 

that are considered to be more directly affected by the 

chemical composition of the claypile generally are 

listed first in the table in order to facilitate examina-

'

Compound or element

CaO

(percent)

Na2O K2O 

(percent) (percent)

CarbonP2O5 Total C ate C 

(percent) (percent) (percent)

Organic C As B* Ba* 

(percent) (ppm) (ppm) (ppm)

Be* 

(ppm)

Cd Ce* 

(ppm) (ppm)

Co* 

(ppm)

Cr* 

(ppm)

Large claypile

0.3 

.1 

.3 ie'

.4 

32

5.9

.6 

.6

........ 

.2 

.5

0.13 

.14 

.09 

.02 

.02 

.01 

C01

.13

.04 

.03

.0001 

.09 

.16

.11

3.6 

2.9 

2.9 

.4 

.5

2.1

1 

.9

2.1

4.3

2.7

0.5 

.3 

.3 

.1 

.1 

.3 

<.05

5.9

.3

.2

.5 

.2

.3

0.6

.88 

.6 

37.8 

3.3 

7.24

.51

2.34 

1.02

0.06 

.01 

.01 

.06 

3.3 

.2

.13

0.5 ........ 70 

.9 8.6 50 

.6 6.4 50 

37.7 ........ <20 

<.l ........ <20 

7.2 .3 <20 

........ <1 <20

.5 6.8 50 

........ 6.7 20

........ 13.4 20

........ ........ <20

........ 12.9 50

2.3 8.0 70 

.9 9.1 70

500 

200 

150 

30 

30 

30 

10

500

70 

100

1.5 

300 

300

300

3 

3

2 

3 

1.5

3

5

7

15 

3 

3

3

<1 300 

<1 150 

<1 150 

.5 <150 

.5 <150 

<1 <150 

<1 <150

<1 300

<1 <150 

<1 <150

<1 <150 

<1 150 

<1 300

<1 300

7 

3 

3 

3 

30 

<3 

<3

<3

50 

70

200 

15 

10

15

300 

150 

300 

70 

30 

7 

2

150

70 

50

15 

150 

200

200

Small claypile

'.2 

.2

0.36 

.10

.14

2.5 

2.9

2.7

0.2 

.2

.2

0.71 

.44

2.99

0.09 

.01

0.6 ........ 70 

.4 2.1 70

3.0 5.6 70

200 

200

200

2 

3

3

<1 300 

<1 300

<1 300

5

7

15

300 

300

200

Claypit

0.2

29 

.4 

.6

0.08

.02 

.63 

.75

1.3

.3 

1.4 

1.6

0.1

<.05 

.05 

.1

0.32

11.8 

.83 

.37

<0.01 

11.3

0.3 5.4 30

.5 2.4 <20 

.8 6.5 30 

.4 12.5 20

30

30 

500 

700

2 

1.5

<1 <150

<1 <150 

<1 <150 

<1 <150

15

5

7 

7

200

7 

30 

70

Soils from vicinity of claypit

0.4 

.5 

.5 

.4 

.2 

.6 

.5 

.2

.5 

.3

.3 

.4 

.3 

.8

1.05 

1.08 

.94 

1.03 

.94 

1.06 

1.01 

.88

.81 

.9

.09 

.06 

.08 

.11

2 

1.8 

1.9 

1.8 

2.1 

1.6 

1.8 

1.8

1.7 

1.9

2.9 

4.7 

2 

4

0.1 

.2 

.2 

.2 

.1 

.2 

.1 

.1

.1 

.3

.3 

.07 

.2 

.3

1.91 

2.6 

1.88 

1.25 

1.17 

1.82 

1.32 

2.05

1.48 

1.16

.33 

3.41 

.46 

.53

0.1 

.11 

.11

.07 

.08 

.06 

.12 

.08

.01 

<.01

<.01 

.02

ioe

1.8 ....... 30 1,000 

2.5 ....... 50 700 

1.8 ....... 30 700 

1.4 ....... 30 700 

1.1 ....... 50 700 

1.8 ....... 30 700 

1.2 ....... 50 700 

2 ....... 50 700

1.5 7.9 30 500 

1.2 5.5 30 700

.3 1.2 70 300 

3.4 1.4 70 300 

.5 6.9 70 200 

.5 2.7 70 300

1.5 

1 

1

1

3 

2 

3 

3

<1 150 

<1 150 

<1 150 

<1 150 

<1 150 

<1 150 

<1 150 

<1 150

<1 <150 

<1 <150

<1 300 

<1 150 

<1 700 

<1 300

15 

15 

15 

15 

15 

15 

15 

5

15

10

7 

7 

30 

10

70 

70 

70 

70 

70 

70 

70 

70

50 

50

300 

300 

200 

200
10 GEOCHEMICAL ANOMALIES OF A CLAYPIT AREA, MISSOURI

TABLE 2. Compounds and elements in samples of surficial

Compound or element

Sample 

No.

Laboratory 

No.

Cu2 

(PPm) (ppm)

F Ga* 

(percent) (ppm)

Gd* 

(PPm)

Hg 

(ppm)

La* 

(PPm)

Li 

(ppm)

Mn* 

(PPm)

Mo* 

(PPm)

Large claypile

i

2 

3 

4 

5 

6 

7 

8 

9 

10 

11 

12 

13 

14

D149910..............._...........

D150439.......... _ .......

D150448............................

D149912 . .. ......

D149913... ................ ....

D150447...................... _

D150433

D150450 .................

D150434

D150435............................

D150436............................

D150437.................... . ...

D154026............................

D154027............................

______ ......... 70

............................ 100

............................. 50

. . .... . 50

........ _ . .. . 70

............................. 15

30

700

700

............................. 2,000

............................. 300

..... 100

..................... 150

"<60

<50

""so

<50 

<50 

<50 

<50 

<50 

<50

".03"

.11

<V6oT

<.001 

.084 .11

.17

.096 

.12 

.1

50 

30 

50 

7 

<5 

15 

<5 

50 

20 

20 

50 

50 

70 

70

........

<50

""so

<50 

<50 

<50 

<50

<50 

<50

0.08 

.17 

.12 

1.3 

.75 

.48 

.15

!34 

.27

"".26 

.06 

.06

150 

70 

100 

30 

30 

<30 

<30 

150 

30 

30 

<30 

100 

150 

150

153 

242 

258 

78 

22 

10 

<5 

195 

180 

156 

1.6 

210 

150 

242

30 

20 

7 

3 

50 

5

3 

30 

50 

100 

15 

100 

700

<3 

3 

15 

7 

<3 

3 

<3 

<3 

<3 

<3 

<3 

5 

3 

3

Small claypile

15 

16 

17

D149911..................... .....

D154024............................

D154025............................

.... .............. ... 30

............................. 50

............................ 50

<50

.098 

.084

50 

70 

70

<50 0.11 

.03 

.02

150 

70 

70

320

284 

280

7 

30 

300

7 

3 

3

Claypit

18 

19 

20 

21

D150445 . ..... ........

D150446.................... ..

D150442 . ._. ....

D160449............................

............................. 150

.. . .... ... . . 10

_ .............. ... 10

............. .... ... .. 20

zz 0.084 

.034 

.022 

.052

50 

<5

10 

20

0.06 .'07

.04

70 

<30 

30 

30

338 

<5 

22

27

50 

150 

500 

150

7 

<3 

<3 

<3

Soils from vicinity of claypit

22

23

24

25

26

27

28

29

30

31

32

33

34

35

D149914.................... ... ...........

D149915..................... . ..........

D149916 .. .

D149917... ................

D149918..... .............. .......... ..

Dl 49919....................... ...... _ .

D149920 . .. .............

D149921... ................

D150440.................... . . .

D150441.....................................

D154028.....................................

D154029............................... ... .

D154030..............._..

D154031....................

.................. 15

.................. 15

20

.................. 20

. .. .. 7

10

.................. 10

.................. 7

.................. 10

.................. 15

... . 100

.................. 70

.................. 50

................. 30

. . .00

.01

<50 .09

.12

.08

.12

15 ........

15 ........

20 ........

20 ........

10 ........

15 ........

15 ........

15 ........

5 10 ........

i 10 ........

70 <50

70 ........

2 50

50 ........

0 04

.07

.06

.05

.04

.05

.05

.07

.09

.08

.02

.02

.05

.02

50

70

70

50

50

70

50

30

50

70

150

70

300

150

24

24

25

24

21

20

23

20

22

22

246

41

148

144

1,000

1,500

500

700

500

1,000

1,500

200

1,500

1,000

15

20

70

70

<3

<3

<3

<3

<3

<3

<3

<3

<3

<3

3

3

7

3

tion of the table for anomalous element concentrations 

in plants.

Plant species have inherent abilities to concentrate 

certain elements in their tissues. This ability varies 

among different species in such a manner that normal 

levels of certain elements in one species may be highly 

anomalous in another. Superimposed on this inherent 

ability of species is their tendency to increase their 

absorption of some of the elements that are unusually 

abundant in the soil on which they grow. Both of these 

characteristics of species must be taken into account 

when seeking to identify anomalous element concentrations in plant tissues that may be related to anomalous 

levels of the same elements in the soil.

Ideally, data on the typical concentrations of elements in plants that are to be used for identifying 

anomalous concentrations should be established for 

each species, on the basis of analyses of plants that 

grew in an environment that was typical for the species. 

Because of the large number of plant species that may 

be of interest in the geochemical study of a suspected 

anomalous area, completely satisfactory data of this 

sort are not commonly available. Therefore, the best 

available data must be used, with the result that the 

typical values that are established for each species or 

group may range from highly reliable to doubtfully 

applicable as bases for identifying anomalies. This variation in reliability of typical values was found in our 

study of the plant species that grew in the claypit area. 

The data that were used for establishing typical values 

(table 8), arranged in order of most reliable to least 

reliable, are discussed in the paragraphs that follow.

In earlier biogeochemical studies in Missouri, we 

established estimates of typical element concentrations 

in three species of woody plants that are widespread in 

the, State, and that grow in the claypit area. These 

species (white oak, buckbrush, and smooth sumac) are 

common in the Oak-Hickory Forest, a vegetation type 

mapped by Kiichler (1964) in which the Callaway 

County claypit area is located. Typical ranges of element concentrations for the three species are presented 

in table 8.

Redcedar is another species which grows in the claypit area and for which we have estimates of typical 

element concentrations. These estimates (table 8) are 

based on analyses of 10 samples from the Oak-Hickory 

Forest area.

In certain species for which we do not have adequate 

data, the normal element concentrations can be estimated by using the analyses of closely related species; 

this procedure is based on the assumption that the element-concentrating ability among species is related to 

their degree of taxonomic affinity, which may be generally, but not invariably, true. For example, data are
RESULTS AND DISCUSSION 11

deposits and efflorescent salts from the claypit area Continued

Compound or element

Nb* 

(ppm)

15

10 

10 

<10

<10

<10

<10 

<10 

<10 

<C10

10 

15 

15

15

20 

20

10

10

Nd* 

(ppm)

150

100 

100 

<70

<70

"200 

<70 

<70 

<70

100

150 

150

150

70 

100

70

<70

<70

Ni* 

(ppm)

100

50 

30 

20

150

15

<5 

30 

300 

500 

1,500

100 

100 

100

70

100 

100

100

20

7

50

Pb* 

(ppm)

30

30 

50 

70

15

30 

15 

15

30 

50

70

50

30 

50

20

15

15

Pr* 

(ppm)

<100 

<100

'"iob

<100 

<100

<100 

<100 

<100

<100 

<100

<100

Sc* 

(ppm)

30

30 

30 

15

10

<5

<5 

30 

15 

15 

10

20 

30 

30

50

30 

30

30

<5

7

10

Se 

(ppm

4

3.2

1.7

.5 

.6 

3.6 

4.8

6.7 

2.3 

2.3

3

1.6 

1.8

0.4

1

.2

.2

Sm* 

) (ppm)

Large claypile

<100

<100 

<100 

<100

<100

""iob

<100 

<100

<100 

<100 

<100

Small claypile

<100

<100 

<100

Claypit

<100

<100

<100

Sr* 

(ppm)

2,000

700 

700 

70

70

30

70 

2,000 

150 

150 

<5

1,500 

1,000 

1,000

700

700 

700

150

150

100

150

Ti* 

(percent) (

1

.3 

.5 

.15

.15

.02

.002 

.5 

.2 

.15 

<.0002

.3 

.7 

.5

1

.7 

.7

0.5

.01

.3

.2

V* 

ppm)

QAA

300 

700 

500

50

10

<7 

200 

70 

70

<7

200 

300 

300

700

500 

300

500

15

50

100

Y* 

(ppm)

50

70 

50 

50

70

15

CIO 

150 

70 

100 

150

70 

70 

70

70

50 

50

20

30

30

Yb* 

(ppm)

5

7 

5

7

7 

7 

7 

15

7 

7 

7

7

5

7

3

3

3

Zn

(ppm)

35

31

27 

132

17

12

<5 

20 

33 

31 

1.7

48 

47 

32

26

30 

30

31

8

39

77

Zr* 

(ppm)

150

150 

150 

30

30

10

100 

70 

70

100 

150 

150

150

150 

150

150

300

200

Soils from vicinity of claypit

10

10

10

10

10

10

10

10

10

10

20

20

20

50

70

70

70

70

70

70

70

70

<70

70

200

70

300

150

15

20

15

15

15

15

15

15

15

7

70

70

50

70

15 .... . 10

20 .... 7

30 .... 15

30 .... 15

15 ... 7

30 ... 7

20 ... 7

15 ... 7

20 ... 7

15 .... 7

70 <100 30

30 <100 20

30 <100 30

30 <100 30

0.3

.6

.6

.7

.2

.4

.2

.3

.6

.5

.7

.9

2.8

1.2

<100

<100

<100

<100

<100

<100

<100

<100

<100

<100

<100

<100

<100

<100

200

150

200

200

150

150

150

150

150

150

700

500

1,000

1,000

0.3

.3

.5

.5

.5

.5

.5

.5

.3

.5

.7

.7

.7

.7

100

70

150

150

70

70

100

70

70

50

700

150

300

300

30

30

30

50

30

30

30

30

50

50

70

50

50

50

3

5

3

7

3

3

3

3

5

5

7

5

7

5

49 300

52 300

67 300

56 200

34 300

44 300

43 300

39 300

47 300

29 500

31 150

36 200

24 150

38 150

not available in our files or in the available literature 

on which to establish typical element concentrations 

in white sweetclover; however, we do have data on the 

element content of 10 samples of yellow sweetclover, a 

closely related species, from other parts of the United 

States. In the absence of better estimates of the normal 

values, these data are given in table 8 for use in evaluating the element content of white sweetclover samples 

from the claypit area.

Certain element-concentrating capabilities are characteristic of many species within a plant family, and 

somewhat predictable differences in these abilities may 

occur among families. We have seven samples of grasses 

from the claypit area, but have no highly reliable means 

of estimating a corresponding norm for use in identifying anomalous values. If we assume that members of 

the Grass Family tend to concentrate elements similarly, analytical data obtained for 18 samples of 

meadow fescue from locations throughout Missouri, 

as given in table 8, may be used for judging anomalies 

in the claypit grass samples.

If corresponding analytical data for certain species 

sampled in the claypit area are unavailable, there may 

be no reliable basis for judging anomalous element concentrations in these species. Nevertheless, we do have 

estimates of typical element values, and ranges in 

values, for plants in general; these estimates are based

on about 1,100 plant samples, including many different 

species, from throughout the conterminous United 

States. These samples were collected in a nationwide 

study of soils, described by Shacklette, Hamilton, 

Boerngen, and Bowles (1971). The values, given in 

table 8, may be used for identifying extremely high or 

extremely low concentrations of elements in plant 

samples from the claypit area if no better means for 

such identifications are available.

Anomalies in the elemental compositions of the 

plants growing in the claypit area are recognized by 

comparing their analyses as given in table 3 to the 

typical values (central 95-percent range) listed in table 

8. The following discussion of these anomalies is organized by species or plant type, and the sample numbers 

refer to those in table 3.

Five white oak trees were sampled on a traverse 

extending from the margin of the larger claypile to the 

wall of the claypit and down the drainage system to the 

area in which cattle had been pastured. Cadmium was 

unusually highly concentrated in all the samples except 

No. 3, and sodium was abnormally low in all the 

samples (table 3). Elemental compositions of the 

samples from the trees most closely associated with the 

claypile (Nos. 1 and 2) were the most divergent from 

typical values. In general, these samples had positive 

anomalies in concentrations of aluminum, cadmium,
12 GEOCHEMICAL ANOMALIES OF A CLAYPIT AREA, MISSOURI

had additional positive anomalies in chromium, copper, 

gallium, scandium, titanium, vanadium, and ytterbium. 

The scandium anomaly in this sample is unique; no 

other sample collected from the area contained detectable amounts of this element.

Of all the plants sampled, only redcedar contained 

detectable beryllium. This element was found in 

samples of the claypile, and analyses of water samples 

and efflorescent salts showed that it was moving from 

this source. Beryllium is not commonly detected in 

plant samples. Of about 900 samples of various plant 

species from throughout Missouri, only eight contained 

2 ppm or more beryllium, and of these eight samples, 

all were of shagbark hickory (Carya ovata) trees 

except one which was of smooth sumac. No beryllium

TABLE 3. Ash yield and elemental composition

[Analysts: Harriet G. Neiman, Thelma F. Harms, and Clara S. E. Papp. ............. no data available. Ash, As, Hg, and Se reported as percent or ppm in dry

cobalt, copper, potassium, lanthanum, molybdenum, 

nickel, ytterbium, and zinc. Negative anomalies were 

apparent for barium, calcium, and sodium. Several 

anomalies, unique to samples of white oak, were the 

low calcium levels in the samples from site 1 near the 

claypile, the only lanthanum anomaly (sample 1), and 

the abnormally high zinc values in samples 1 and 4, collected from the pasture site. The most extreme positive 

anomalies were reflected in the cobalt, copper, molybdenum, and nickel concentrations in these samples.

Both samples of redcedar from near the claypiles contained unusually high levels of aluminum, beryllium, 

cobalt, and nickel, and unusually low levels of barium 

and sodium. Sample 6, collected at site 3 where the 

surficial deposits from the larger claypile were thick,

following equation: element (ppm) in dry material = element (ppm) in ash X

ash content (percent) 

100 . Some elements were looked for in all samples but

follows: Antimony, 300; bismuth, 20; cerium, 300; europium, 200; germanium, 20; gold, 50; hafnium, 200; indium, 20; niobium, 20; palladium, 2; platinum, 

sample, the following elements, with their stated lower detection limits, were looked for in the same sample, but were not found: Neodymium, 150; 

geometric classes, in the series 1, 1.5, 2, 3, 5, 7, 10, 15, and so forth]

Labora- Site Date Sample tory No. sampled 

No- No. (fig. 1) (1971)

Species Plant part sampled Ash ^.1* 

(percent) (percent)

Ash or

As 

(ppml

element

B* 

(ppm)

Ba* 

(ppm)

Be* 

(ppm)

Trees

i

2 

3 

4 

5 

6

7

D415622 

D415623 

D415627 

D415625 

D415630 

D415578

D415579

1 

1 

4 

6 

2 

3

1

June 30 

......do......

......do......

......do......

......do......

May 7 

......do......

White oak (Quercus alba) ........ 

....... do ..........................................

........ do ..........................................

........ do ..........................................

........ do ..........................................

Redcedar 

(Juniperua virginiana) ........ 

........ do ..........................................

Branches, terminal 8-10 in..... 

........ do ........................................

........ do ........................................

........ do ........................................

........ do ........................................

Branches, with leaves.. ............ 

........ do ........................................

2 

3 

3.8 

3.2 

3.5

3.7 

4.5

0.7 

.7 

.3 

.2 

.15

7 

1.5

<0.25 

<.25 

<.25 

<.25 

.25

<.25 

<.25

300 

200 

200 

200 

150

200 

200

500 

1,000 

3,000 

3,000 

2,000

500 

150

<2 

<2 

<2 

<2 

<2

3 

2

Shrubs

8

9 

10 

11 

12 

13 

14

D415621

D416626 

D415624 

D415629 

D415692 

D415620 

D415628

1

4 

6 

2 

10 

1 

2

June 30 

......do......

......do......

......do......

Sept. 28 

June 30 

......do......

Buckbrush (Symphoricarpoa

........ do ..........................................

........ do ..........................................

........ do ..........................................

........ do ..........................................

Smooth sumac (Rhus glabra).. 

do .

........ do ........................................

........ do ...................... ...............

........ do ........................................

........ do ........................................

........ do ........................................

2.4 

2.3 

2.2 

2.5 

2.2 

3 

3.2

1.5 

1.5 

.7 

1.5 

3 

.2 

.5

<0.25 

<.25 

<.25 

<.25 

<.25 

<.25 

<.25

200 

150 

100 

150 

200 

200 

200

5,000 

2,000 

2,000 

3,000 

3,000 

7,000 

3,000

<2 

<2 

<2 

<2 

<2 

<2 

<2

Grasses and sedges

15 

16 

17 

18 

19

20 

21

D415641 

D415643 

D415642 

D415648 

1)415649

D415651 

D415647

2 

9 

9 

18 

18

18 

18

June 17 

......do......

......do......

......do......

......do...... 

......do......

......do......

Wood reed grass

Fowl meadow grass

Common bullrush

Meadow fescue

Timothy (Phleum pratenae) 

and Japanese chess

Bluegrass (Poa pratensis) and

Timothy, meadow fescue, and 

redtop (Agrostis alba) ..........

........ do ........................................

........ do ......................................

........ do ........................................

........ do ........................................

........ do ........................................

........ do ........................................

10 

7.4 

7.4 

8.4

16 

9.7 

11

0.5 

.5 

.5

.7

5 

1

.7

<0.25 

<.25 

<.25 

<.25

.5 

<.25 

<.25

50 

50 

100 

70

100 

70 

50

200 

200 

300 

200

700 

500 

1,000

<2 

<2 

<2 

<2

<2 

<2 

<2

Forbs

22 

23

24 

25

26

27 

28 

29 

30 

31 

32 

33 

34

D415639 

D415644

D415650 

D415646

D415640

D415684 

D415685 

D415686 

D415687 

D415688 

D415689 

D415690 

D415691

2 

9

18 

12

2

1 

1 

2 

4 

5 

5 

4 

4

June 17 

......do......

do

......do......

......do......

Sept. 26 

......do......

......do......

......do......

Sept. 28 

......do...... 

......do......

......do......

Goldenrod (Solidago sp. ).......... 

Common plantain

do

White snakeroot

White sweetclover

........ do ..........................................

.... do

........ do ..........................................

..do

. . .... do 

........ do ..........................................

Japanese clover 

(Lespedeza striata) ..............

........ do ........................................

........ do ........................................

do ... ......... .......... .............

2d-yr. green stems and leaves 

2d-yr. dead stems and seeds.... 

........ do ........................................

........ do ........................................

Ist-yr. green stems and leaves 

........ do ......................................

Ist-yr. roots .............................. 

Ist-yr. green stems and leaves

Above-ground parts ................

11

14 

13

18

10 

2.9 

2.3 

2.1 

7.2 

8 

3.8 

7.2

5.2

1

.5 

1

1.5

.1 

1 

1 

1.5

.7 

3 

5 

3

2

<0.25

<.25 

.25

<.25

<.25 

.25 

<.25 

<.25 

<.25 

.25 

<.5

<.25

150

150 

150

100

150 

300 

700 

300 

300 

300 

150 

300

200

150

2,000 

700

1,500

1,000 

1,000 

300 

500 

70 

200 

150 

150

500

<2

<2 

<2

<2

<2 

<2 

<2 

<2 

<2 

<2 

<2 

<2

<2

Aquatic plants

35 

36

D415638 

D415645

2 

12

June 17 

......do......

Cattail (Typha latifolia) .......... 

........ do .......................................... ........ do ........................................

6.7 

10

0.1 

.1

<0.25 

<.25

70 

70

70 

3,000

<2 

<2
RESULTS AND DISCUSSION 13

was found, however, in any of the 110 samples of redcedar collected from throughout Missouri in an earlier 

study. If this plant is, in fact, a beryllium accumulator, 

high soil concentrations of this element appear necessary for the accumulation to occur.

Buckbrush samples, collected at the white oak 

sampling sites, generally contained positively anomalous concentrations of molybdenum and nickel, and 

negatively anomalous amounts of sodium. Cadmium 

occurred in unusually high concentrations in the two 

samples (Nos. 8 and 9) from nearest the larger claypile. Abnormally high concentrations of aluminum, copper, gallium, tin, and vanadium were found in the single 

sample that was collected in September (No. 12). 

Anomalous concentrations of iron, potassium, manganese, lead, and titanium occurred in other samples of 

this species.

Smooth sumac, as indicated by the analyses on table 

3, is much less sensitive to the element content of the 

underlying soils than is white oak, an observation consistent with the conclusions of Shacklette, Sauer, and 

Miesch (1970, p. C25). In the two sumac samples, only 

cadmium and cobalt occurred in unusually high concentrations, and sodium occurred as a negative anomaly. Molybdenum was abnormally high in sample 13 

collected at the edge of the claypile, and magnesium 

was anomalous in sample 14 collected from the wall of 

the claypit.

Of the six samples of grasses that were collected in 

the claypit area, only sample 19, from Ranch B, conof plant samples from the claypit area

material. Other elements reported as ppm or percent in ash; these values in ash can be converted to approximate values in dry material by using the 

were not found. These elements, analyzed by the semiquantitative spectrographic method, and their lower detection limits, in parts per million, are as

70; rhenium, 70; silver, 1; tantalum, 500; tellurium, 5,000; thallium, 100; thorium, 500; tungsten, 200; and uranium, 1,000. If lanthanum was found in a 

praseodymium, 200; and samarium, 200. Asterisk, analysis by a semiquantitative spectrographic method. Results are reported as geometric midpoints of

Ca

(percent)

22

26

30

31

32

22

23

16

15

12

12

15

23

21

3.4

3.6

4.6

3.2

6

4.4

2.4

8.6

15

4.2

22

16

29

25

16

14

4.3

11

17

10

6.8

Cd

(ppm)

10

11

6.2

7.4

8.4

9

5.4

45

35

10

28

14

5.2

4.8

0.4

.3

.9

.3

.3

1.2

.5

2

1

.9

1.2

.8

9.2

3.2

3.3

1.0

.8

0.3

.4

Co

(ppm)

60

60

4

4

7

20

25

6

8

2

8

5

9

5

2

1

1

3

7

2

1

14

2

9

15

4

28

17

14

3.5

8

15

10

<5

8

20

Cr*

(ppm)

7

3

5

2

2

50

20

15

20

10

30

50

5

5

7

7

7

7

50

7

5

15

3

20

15

2

10

15

30

15

50

70

50

30

3

<2

Cu*

(ppm)

500

200

150

150

100

200

70

300

150

150

100

1,000

150

50

50

30

50

30

50

50

50

150

100

50

100

50

150

200

1,500

300

1,000

200

200

700

100

50

Fe*

(percent)

0.3

.2

.3

.15

.1

1

.5

0.7

.5

.2

1

.7

.1

.2

0.15

.15

.1

.3

2

.3

.3

0.3

.15

.5

.5

.1

.2

.3

.5

.15

.5

.7

.7

.7

0.1

.2

Ga*

(ppm)

<5

<5

<5

<5

<5

7

<5

<5

<5

<5

<5

10

<5

<5

<5

<5

<5

<5

7

<5

<5

<5

<6

<5

<5

<5

<5

<5

<5

<5

<5

10

<5

<5

<5

<5

Ash or element

Hg K

(ppm) (percent)

Trees

<0.025 13

<.025 9.8

<.025 6.4

<.025 7.4

<.025 8

.025 11

.025 9.2

Shrubs

<0.025 17

<.025 22

<.025 25

<.025 18

.025 17

<.025 15

<0.25 17

Grasses and sedges

<0.025 17

.025 20

<.025 24

.025 26

.......... 14

.025 26

.05 28

Forbs

<0.025 26

.025 22

.05 29

<.025 17

<.025 19

<.025 6.6

<.025 8.4

.025 21

.025 17

.......... 27

<.05 20

.025 12

Aquatic plants

<0.025 29

.025 30

La*

(ppm)

70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

<70

Li

(PPm)

20

16

4

<4

4

40

18

8

16

<4

12

22

4

<4

220

4

4

4

12

<4

14

12

<4

<4

<4

<4

22

6

12

10

16

28

8

16

4

<4

Mg*

(percent)

3

2

3

3

1.5

2

3

3

2

3

5

3

2

5

0.7

3

2

3

5

3

2

2

5

7

1.5

5

3

3

5

3

3

5

5

5

2

3

Mn*

(ppm)

30,000

30,000

20,000

10,000

20,000

15,000

15,000

20,000

15,000

3,000

20,000

7,000

1,500

1,500

1,500

700

1,500

1,000

1,500

1,000

1,000

2,000

500

1,500

7,000

300

500

500

500

300

700

500

700

7,000

15,000

20,000

Mo

(ppm)

10

10

4

4

<4

<5

<5

10

10

10

<4

20

10

4

10

10

4

10

10

4

<4

10

<4

4

60

10

60

750

180

40

250

50

50

10

10

Na

(percent)

0.04

.04

.04

.04

.03

.07

.08

0.06

.06

.06

.11

.22

.03

.02

0.02

.03

.03

.12

.09

.07

.12

0.03

.03

.04

.06

.05

.17

.18

.27

.13

.19

1.8

.26

.15

0.88

.6

Ni*

(ppm)

200

200

70

30

50

300

300

50

50

7

50

30

30

20

20

5

7

7

7

10

20

50

7

10

15

30

100

50

70

50

30

70

70

150

30

15
14 GEOCHEMICAL ANOMALIES OF A CLAYPIT AREA, MISSOURI

TABLE 3. Ash yield and elemental composition of plant samples from the claypit area Continued

Sample 

No.

1

2

3

4

5

6

7

8

9

10

11

19

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

Laboratory 

No.

D415622...................

D415623..................

D415627..................

D415625................

D415630..................

D415578..................

D415579...................

D415621..................

D415626..................

D415624..................

D415629..................

D415692. ................

D415620...................

D415628..................

D415641..................

D415643..................

D415642..................

D415648..................

D415649..................

D415651..................

D415647.................

D415639..................

D415644..................

D415650..................

D415646..................

D415640..................

D415684..................

D415685..................

D415686..................

D415687..................

D415688..................

D415689..................

D415690..................

D415691..................

D415638..................

D415645..................

P 

(ppm)

............ 24,000

............ 24,000

............ 18,000

............ 12,000

............ 12,000

............ 12,000

............ 24,000

............ 18,000

............ 18,000

............ 24,000

............ 24,000

............ 24,000

............ 18,000

............ 24,000

............ 6,000

............ 24,000

............ 18,000

............ 18,000

............ 12,000

............ 24,000

24,000

............ 12,000

............ 18,000

............ 24,000

............ 18,000

............ 12,000

.......... . 18,000

............ 12,000

............ 24,000

............ 18,000

............ 24,000

............ 48,000

............ 18,000

............ 45,000

............ 12,000

............ 24,000

Pb* 

(ppm)

300

200

150

150

70

300

100

500

200

30

300

500

50

50

<20 ^on

f">(\

<20

20

<20

<20

^on

<20

<20 ^">n

<20

70

150

300

100

200

20

20

200

<20

<20

Sc* 

(ppm)

<5

<5

<5

<5

<5

7

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

Ash or element

Se Sn* 

(ppm) (ppm)

Trees

<0.5 <20

<.5 <20

<.5 <20

<.5 <20

<.5 <20

<.5 <20

<.5 <20

Shrubs

<0.5 <20

<.5 <20

<.5 <20

<.5 <20

70

<.5 <20

<-5 <20

Grasses and sedges

0.5 <20

<.5 <20

<.5 <20

<.5 <20

.5 <20

<.5 <20

<.5 <20

Forbs

<0.5 <20

.5 <20

<1 <20

<1 <20

<.5 <20

<f>(\

........ <20

........ 70

........ 20

........ 70

........ <20

........ <20

........ 50

Aquatic plants

<0.5 <20

<.5 <20

Sr* 

(ppm)

1,000

1,000

1,000

2,000

2,000

1,000

500

3,000

1,500

2,000

2,000

2,000

5,000

3,000

200

200

300

200

200

200

300

500

1,500

700

1,000

1,000

1,500

1,000

1,500

700

700

1,000

700

500

700

2,000

Ti* 

(percent)

0.03

.02

.02

.015

.01

.20

.07

0.10

.10

.05

.20

.10

.02

.03

0.02

.02

.02

.02

.20

.05

.03

0.05

.05

.05

.07

.007

.03

.05

.05

.015

.1

.3

.1

.1

0.005

.01

V* 

(ppm)

<5

<5

<5

<5

<5

70

30

20

30

10

50

50

<5

<5

10

10

10

10

70

10

10

20

<5

20

20

<5

<5

<5

20

<5

50

100

50

30

<5

<5

Y* 

(ppm)

<20

<20

^on

^on

<20

<20

<20

^on

<20

<20

<20

9f>

<20

<20

<20

<20

<20

<20

<20

<20

<20

<20

<20

<20

f">(\

<20

<20

<20

<20

<20

<20

20

20

20

<20

<20

Yb* 

(ppm)

2

2

^n

<2

<2

5

<2

<2

2

<2

2

<2

<2

<2

<2

<2

<2

<2

2

<2

<2

<2

<2

<2

<2

<2

<2

<2

<2

<2

<2

2

2

2

<2

<2

Zn 

(ppm)

1,060

380

360

680

400

440

440

1,600

1,000

1,500

2,100

1,550

1,000

680

240

240

260

160

260

470

340

380

360

280

300

220

270

240

420

290

410

520

280

700

220

220

Zr* 

(ppm)

<20

<20 ^9n

<^<M\

<20

50

30

70

50

20

70

70

<20

30

50

<20

<20

20

150

30

20

<20

50

50

70

<20

20

20

20

<20

70

50

50

50

<20

<20

tained anomalous concentrations of elements, all of 

which were positive. These anomalies were in aluminum, boron, cobalt, chromium, iron, gallium, titanium, 

and ytterbium. Inasmuch as the mixture of grasses in 

this sample did not include meadow fescue (the grass 

species used to establish typical values), these unusually high concentrations may be due more to species 

differences in absorption capability than to contamination of the soil.

White sweetclover is of special interest because it 

is a known molybdenum accumulator, and because 

molybdenum was found in anomalous concentrations 

(3-15 ppm) in samples of clay, shale, and alluvium 

from the claypit area. In parts of the Western United 

States where soils contain high levels of molybdenum 

(1.5 ppm or more), severe illness has occurred in cattle 

that grazed this plant (Barshad, 1948). In white sweetclover sample 26 (table 3), collected in June, 60 ppm 

molybdenum was found in the ash (6 ppm in dry matter) , and although this concentration is not considered 

anomalous if judged by the central 95-percent range of 

values for a closely related species (yellow sweetclover, 

table 8), it exceeds the tolerance level of 5 ppm in dry 

matter for cattle that was given by Webb and Atkinson 

(1965). Molybdenum levels in another sample of white

sweetclover (No. 29, table 3) from the claypit area, 

collected in September, exceeded this tolerance level 

by a factor of three. In addition, samples of white 

sweetclover contained anomalous concentrations of 

aluminum, boron, chromium, cobalt, copper, gallium, 

lead, manganese, nickel, tin, and titanium.

Japanese clover (sample 34, table 3) was the only 

other forb (broad-leaved forage herb) sampled that 

reflected the anomalous copper and nickel levels in substrates of the claypit area. This species, like white 

sweetclover, is a palatable forage plant and its element 

content, therefore, is important in searching for causes 

of the metabolic disorders of cattle at this site.

WATER

Chemical analyses of the four samples of water from 

the claypit area are given in table 4. The chemical compositions of surface waters, as were sampled at the 

claypit study area, are greatly influenced by meteorological conditions at a location both before and at the 

time of sampling. Water samples from this area were 

collected June 17, about 1 week after a mild thunderstorm had occurred. During the previous few months, 

however, very little rain had fallen; therefore, the properties of the samples were more representative of water
RESULTS AND DISCUSSION 15

TABLE 4. Physical properties and chemical composition of 

surface water samples from the claypit study area

[Analysts: P. R. Barnett, O. J. Feist, Jr., Darwin Golden, R. L. James, E. C. 

Mallory, Jr., and R. D. McKibben. All samples collected June 17, 1971]

Origin of sample.. Farm pond 

Site No. (fig. 1).... 12

Claypit Small pool in Rocky Branch

Rocky Branch on Ranch B 

2 9 18

Physical properties, at time of collection

Appearance .......... 1 

1 

i 

Temperature °C~.. 

Specific conductance (/imhos/ 

cm at 25°). 

pH ..........................

Medium Bluish green, Light tan, Slightly 

>rown, with murky milky turbid 

nuddy cast 

33.5 29.0 26.9 28.4 

165 830 295 800

7.50 4.27 7.73 8.22

Chemical composition G*g/l, except as indicated)

Al ............................

As ............................

B ..............................

Ba ............................

Be ............................

Bi ............................

Cd ............................

Co ............................

Cr ............................

Cu ............................

Fe ............................

Ga ...

Ge ............................

Li ............................

Mn ..........................

Mo ..........................

Ni ............................

Pb ............................

Rb ..........................

Sr ............................

Ti ............................

V ............................

Zn ..........................

Zr ............................

Organic N 

(mg/1) as N ...... 

NO2 (mg/1) .......... 

NH3 (mg/1) as N 

NO3 (mg/1) ..........

110,000 

4 

250 

1,600 

<4

1 

17 

5 

170 

83,000 

38 

<33 

48 

4,900 

<8 

130 

72 

260 

260 

1,700 

230 

60 

880

3.5 

.17 

.7 

2.3

13,000

19 

90 

10 

<5 

2 

120 

7 

1,400 

300 

<5

60 

1,900 

<3 

470 

8 

2 

220 

6 

2 

210

.07 

0 

.02 

.3

59,000

110 

300

<5

1 

4 

3 

76 

8,000 

17

52 

1,700 

<2 

78 

46 

33 

360 

1,700 

130 

10 

120

1.2 

.01 

.01 

1.3

630

14 

190 

<2 

<5

2 

2 

440 

<5

2 

100 

<3

4

170* 

27 

3 

20

.34 

0 

0 

.2

as it occurs during dry, rather than wet, periods. During 

wet periods the stream waters carry abundant suspended material and, consequently, higher concentrations of the elements that occur in the clay.

The part of Rocky Branch that drains the claypiles 

(fig. 1) was not flowing at the time of sampling, and

TABLE ^. Selected trace elements in whole blood samples from 

beef cattle having interference syndrome and from those 

that were unaffected

[Concentration? given as mg/100 g. Blood samples were drawn on the ranches 

in the forenoon of June 17, 1971, and submitted immediately for analysis]

Cattle having interference syndrome Unaffected cattle 

(controls)

Laboratory 

No. Angus cows, 

Ranch A

Charolais

bull, 

Ranch B

Angus cows, 

Ranch A

Charolais

bull, 

Ranch B

__________Cl-821 C2-875 C3-851 C7-038 C4-422 C5-456 C6-11068

Element

Al .................. <0.25

Co

Cu

Fe.

Mn

Mo

Zn

<.05 

.088

1.83 

.010 

.050

1.11

<0.25 

<.05

.080 

1.74 

.010 

.050 

.97

<0.25 

<.05

.070 

1.84 

.010 

.050 

1.22

<0.25 

<.05

.067 

2.04 

.010 

.050 

.95

<0.25 

<.05 

.067 

2.04 

.010 

.050 

.95

<0.25 

<C05 

.071 

2.04 

.010 

.050 

2.04

<0.25 

<.05 

.071 

2.04 

.010 

.050 

.95

the only water in the creekbed occurred in isolated 

pools. Therefore, water from the claypit pond and the 

claypiles was not reaching Ranch B. However, during 

periods of intense rainfall water from the claypit area 

does flow through this ranch, as indicated by the clay 

coatings on many rocks in the streambed. Rocky 

Branch is springfed at Ranch B, and at the time of 

sampling was flowing at an aproximate rate of 1 cubic 

foot per second.

The only basis available for judging any possible 

abnormalities in the compositions of surface waters 

collected from the claypit area is an analysis (table 4) 

of a sample from the farm pond at site 12 (fig. 1). The 

sample collected and analyzed contained a large quantity of suspended silt and clay and, therefore, represents stock water about as impure as it occurs under 

normal conditions. The pond, however, received no 

drainage from the claypit or the claypiles adjacent to it.

The acid water in the claypit, as is evident from the 

data in table 4, contains unusually high concentrations 

of several elements, including beryllium, cobalt, copper,

TABLE 5. Breeding and calving history of three distinct beef cattle herds on Ranch A for the 1970 and 1971 breeding and

calving seasons

[All cows were pasture bred; bulls remained in the pasture from June to September, therefore most cows calved during March and April of the following year. 

Numbers in parentheses are percentages. Herd No. 2 ranged on pasture affected by the claypile; herds 1 and 3 were kept on unaffected pastures. The breed 

of Herds 1 and 2, designated "Angus" in 1970, was changed to "Angus-Charolais" in 1971 because the sires were changed from Angus to Charolais]

No.

1 

2

Herd

Breed

Angus 

......do......

Breed

Angus 

......do.....

Sires

Number

3 

. 1

Age 

(yrs)

7 

2

Dami

Breed

Angus 

......do......

;

Age 

(yrs)

7 

4

Bred

1970

54 

66

Cows

Calved

54 (100) 

36 (54.5)

Cah

Born alive

54 (100) 

31 (86.1)

ires

Stillborn

0(0) 

5 (13.9)

Comments

Brought to ranch in 1966. 

Brought to ranch Oct. 1969

already bred; 7-8 cows 

rebred.

1971

1 Angus-Charolais Charolais 1 9 Angus 8 54 54(100) 54(100) 0(0) One calf died soon after

birth.

2 ......do...... ......do...... 1 5 ......do...... 5 66 24 (36.5) 23 (95.8) 1 (4.2) Undersized dam of stillborn calf died soon after 

calving.

3 Charolais ......do...... 1 4 Charolais 4 24 24(100) 24(100) 0(0) Two cows had difficulty

calving, but recovered. 

Artificial insemination, 

in addition to pasture 

breeding, was used.
16 GEOCHEMICAL ANOMALIES OF A CLAYPIT AREA, MISSOURI

TABLE 7. Concentrations of biochemic constituents in blood serum from beef cattle having interference syndroms and from those

that were unaffected

[Blood samples were drawn on the ranches in the forenoon of June 17, 1971, and submitted immediately for analysis, mg/100 ml=milligrams per 100 milliliters;

mEq/l=milliequivalents per liter; g/100 ml=grams per 100 milliliters]

Cattle having interference syndrome

Constituents of serum and reporting units

Cholesterol, mg/100 ml ....................................

Calcium, mg/100 ml............................... ...........

Chloride, mEq/1................................................

Total bilirubin, g/100 ml..................................

Total protein, g/100 ml....................................

Alkaline phosphatase, King- Armstrong 

Unitsi ........ ......................................................

Glutamic-oxaloacetic transaminase, 

King Units1 ....................................................

Angus cows, Ranch A ChwoW. bull,

C 1-821

... 154

9.8

97

.4

1.0

7.4

7.2

25

... 572

19

... 124

.. 149

6.3

C2-875

128 

9.4 

96 

.3 

1.0 

6.6 

5.9 

21 

530

18

140 

143 

4.8

C3-851

126 

9.3 

98 

.3 

1.0 

7.4 

6.2 

18 

576

17

116 

150 

5.6

C7-038

95 

9.6 

97 

.5 

.7 

7.0 

7.9 

14 

511

28

127 

152 

4.9

Unaffected cattle (controls)

Angus cows, Ranch A

C4-422

170 

9.2 

99 

.4 

.3 

7.6 

5.9 

24 

547

20

116 

146 

4.6

C5-456

128 

9.3 

98 

.4 

.4 

7.7 

5.5 

26 

455

16

112 

149 

5.2

Charolais bull, 

Ranch B

C6-11068

87

9.7 

96 

.5 

.9 

6.7 

7.0 

18 

403

27

106 

147 

5.6

l Tumbleson (1969).

nickel, and zinc. Samples collected downstream from 

the claypit, however, contained no concentrations of 

elements that were notably high with respect to the 

water in the farm pond at site 12.

Because samples of whole water were collected and 

analyzed, it is not known whether the elements present

are in solution or in suspended particles. However, the 

low pH (4.3) of the claypit water may cause many elements in the suspended particles to occur in soluble 

form.

The question as to whether elements occur in soluble 

form or within suspended materials may be important

TABLE 8. Mean chemical compositions, with central 95-percent range,

[These data were used for establishing ranges in typical chemical compositions of certain sampling media. GM, geometric mean; GD, geometric deviation; ratio,

per million.

Element or compound

Al, or ALOj, percent1 . ..........................................

B .................................................................................

Be ................................................................................

C, total, percent ........................................................

C, carbonate, percent ..............................................

C, organic, percent ..................................................

Ca, or CaO, percent1 ........................................... ...

Cd

Ce ....................... .. ........................._......................,

Cr

Cu ... .................. .....................................................

Fe, or total Fe as FeaOa, percent1 .......................

Ga ................................................................................

Hg .... .

K, or KzO, percent1 ..................................................

La ........ _ . . ... .... .............

Li ...................... . . . ............. ................... .........

Mg, or MgO, percent1 ..............................................

Mn .............................................................................

Mo ................................................................................

Na, or Na2<D, percent1 ............................................

Nb ...............................................................................

Nd .............................................................................

Ni ...............................................................................

P, or P2Os, percent1 ................. ...............................

Pb ...................

Sc .... ...........

Se ........................ ........... ......................

Si, or SiOa, percent1 ................................................

Sr ....................... .. .. ..... .

Ti, percent ................................................................

v

Y ........ ... ... ...

Yb ............... .....

Zn .................................................................

Zr ................................................................................

B-horizon soils from Oak-Hickory Forest 

vegetation type

GM

................. 5.1

................. 39

QQA

................. .77

................. 1.1

................ .054

................. .96

................. .21

................. <1

................. 78

................. 10

A*}

................. 13

................. 2.7

................. 8.4

................. .055

................. 1.3

................. 35

................. 18

................. .30

................. 730

................ <3

................. .38

................. 8.0

................. 47

................. 12

................. .076

................. 23

................ 5.4

................. .31

283

................. 66

................ .35

................. 53

27

................. 2.8

................. 36

................. 300

GD

1.47

1.41

1 78

1.42

1.72

4.14

1.69

2.80

1.45

1.71

1.45

1.99

1.43

1.54

1.91

1.61

1.37

1.33

2.25

2.16

2.01

1.38

1.35

1.82

1.38

1.50

1.49

1.90

37.43

1.66

1.44

1.48

1.50

1.44

1.59

1.63

Central 95-

percent range

2.4-11

20-78

120-1,200

.38-1.5

.37-3.3

.0032-.93

.34-2.7

.027-1.6

37-160

Q A __ OQ

20-90

3.2-51

1.3-5.5

3.5-20

.015-.20

.50-3.4

19-66

10-32

.059-1.5

160-3,400

.094-1.5

4.2-15

26-86

3.6-40

.022-.27

10-52

2.4-12

.086-1.1

"68-97

24-180

.17-.73

24-120

12-61

1.4-5.8

14-91

110-800

Ratio

50:50

49:50

50:50

20:50

50:50

44:50

50:50

46:50

0:50

6:50

49:50

50:50

50:50

50:50

48:50

50:50

50:50

46:50

50:50

50:50

50:50

2:50

50:50

22:50

12:50

47:50

40:50

50:50

37:50

48:50

50:50

50:50

50:50

50:50

50:50

50:50

50:50

50:50

GM

0.19

190

4,200

<2

33

3.7

<300

9 9

130

.14

<5

5.5

<70

1.8

12,000

<5

.15

<20

..........

21

1.3

100

<5

1,800

.016

<5

<20

<2

310

<20

White oak stems

GD

1.62

1.47

1.11

1.33

9 QQ

1.51

1.88

........

1.35

1.86

1.74

1.31

1.80

1.52

1.85

1.59

1.68

........

1.21

Central 95-

percent range

0.072-0.50

88-410

1,700-10,000

27-41

2.1-6.5

.41-12

1.0-12

57-300

.040-.50

3.0-10

.51-6.2

4,000-36,000

.087-.26

6.5-68

.56-3.0

29-340

710-4,600

.0057-.045

....................

210-450

....................

Ratio

50:50

50:50

50:50

0:50

17:17

17:17

0:17

15:17

46:50

50:50

50:50

0:50

17:17

0:50

50:50

50:50

0:50

17:17

0:50

50:50

17:17

50:50

0:50

..........

50:50

50:50

2:50

1:50

0:50

17:17

12:50

See footnotes at end of table.
RESULTS AND DISCUSSION 17

because it bears on the availability of the elements to 

plants and animals. In other words, the environmental 

significance of an occurrence of a trace element in water 

cannot be ascertained from the magnitude of its concentration alone. The lead concentration in the sample 

frpm the control farm pond, for example, is greater than 

that in the other samples; yet the lead that is present 

may be in a form that is not available to animal metabolism, whereas the lead of lesser concentrations in the 

other waters may be readily available. Moreover, many 

elements that were not present in high concentrations 

in the waters from the claypit area at the time of 

sampling may occur in high concentrations during periods of heavy surface runoff. The elements found in the 

precipitate at the base of the claypiles could be expected to occur in solution or as particulate matter in 

waters running off the claypiles during and immediately 

after periods of intense rainfall.

High concentrations of certain microorganisms that 

may occur in water produce toxins to levels that can 

be harmful or fatal to cattle. Some species of blue-green 

algae are especially toxic. The concentration of microorganisms was found to be low in an aliquot of water 

from the claypit; only a few objects that appeared to

be unicellular green algae were found *.y microscopic 

examination (Robert Lipscomb, oral commun., 1971).

BEEF CATTLE

The extent of the interference syndrome in the 

breeding and calving history for the three herds on 

Ranch A is given in table 5. Analyses for trace elements 

in whole blood specimens from herds on both Ranch A 

and Ranch B are given in table 6; analyses for biochemic constituents in blood serum are given in table 7.

We first observed the affected cattle on Ranch A and 

Ranch B in May 1971, although the ranchers had 

noticed interferences with growth, nutrition, and reproduction nearly a year earlier. We advised the ranchers 

to exclude the cattle from the claypit area and the flood 

plain below it by fencing; this was done on Ranch A 

only. At the time of this visit we thought these cattle 

were showing a favorable response to the better ration 

that had been provided and to the spring grass. On 

later visits, however, the cattle were noticed to be 

unthrifty and to be losing weight as the grass became 

short under the influence of a drought in July and 

August, despite supplemental rations that were provided.

of media that are comparable to those sampled in the claypit area

number of samples in which detected : total number of samples; central 95-percent range is calculated as GM-i-GD2 to GMXGD2. Means are given in parts 

except as indicated]

Buckbrush stems

GM

1.2

180

3,800

<2

GD

1.33

1.35

1.63

Central 95-

percent range

0.68-2.1

99-330

1,400-10,000

Ratio

49:49

49:49

49:49

0:49

Smooth sumac stems

GM

0.12

200

3,400

<2

GD

2.11

1.26

2.33

Central 95-

percent range

0.026-0.53

130-320

630-18,000

Ratio

50:50

50:50

50:50

0:50

Redcedar stems and leaves

GM

0.47

210

3,800

<2

GD

1.61

1.30

2.04

Central 95-

percent range

0.18-1.2

120-350

920-16,000

Ratio

10:10

10:10

10:10

0:10

Fescue grass, aboveground parts

GM

0.56

48

340

<2

GD

2.53

1.24

1.72

Central 95-

percent range

0.087-3.6

31-74

110-1,000

Ratio

18:18

14:18

18:18

0:18

15

11

<300

5.2

21

180

.69

<5

15

<70

3.6

10,000

1.4

.24

<20

11

2.2

260

<5

1,500

.12

19

15

1.4

1,300

79

1.21

1.68

1.64

1.57

1.45

1.58

1.24

1.65

1.62

2.49

1 21

1.49

1.31

1.88

1.96

1.73

1.50

1.45

1.42

1.40

2.16

10-22

3.9-31

1.9-14

8.5-52

86-380

.28-1.7

9.8-23

1.3-9.8

3,800-26,000

.23-8.7

.16-.35

5.0-24

1.3-3.8

74-920

.

390-5,800

.040-.36

8.4-43

7.1-32

.69-2.8

660-2,500

17-350

22:22

22:22

0:22

22:22

49:49

49:49

49:49

8:49

22:22

5:49

49:49

49:49

7:49

22:22

0:49

49:49

22:22

49:49

0:49

49:49

49:49

49:49

16:49

13:49

22:22

49:49

24

2.5

<300

1.3

2.7

89

.11

<5

14

<70

2.0

700

<5

.11

<20

4.0

1.7

30

<5

2,700

.013

<5

<20

<2

610

11

1,24

1.32

1.54

1.95

1.43

1.89

1,15

1.43

1.60

1 56

2.82

1.30

2.36

2.19

2.15

1.33

1.85

16-37

1.4-4.4

.55-3.1

.71-10

44-180

.031-.39

11-19

.98-4.1

270-1,800

.045-.27

.50-32

1.0-2.9

5.4-170

560-13,000

.0028-.060

340-1,100

3.2-38

15:15

15:15

0:15

13:15

40:50

50:50

50:50

0:50

15:15

0:50

50:50

50:50

3:50

15:15

0:50

36:50

15:15

37:50

0:50

50:50

50:50

3:50

0:50

0:50

15:15

11:50

28

2.6

<300

<5

9.8

66

.35

<5

<-5

9.8

<70

4.8

5,700

2.3

.27

<20

37

1.9

120

<5

<1

2,300

.030

4.6

<20

<2

480

29

1 13

2.64

1.81

1.71

1.72

1 32

1.42

1.92

2.80

1 65

2.03

1.32

3.25

2.01

2.00

3.10

........

i67

1.89

22-36

.37-18

3.0-32

23-190

.12-1.0

5.6-17

2.4-9.7

1,500-21,000

.29-18

.099-.74

9.0-150

1.1-3.3

11-1,300

570-9,300

.0075-.12

.48-44

170-1,300

8.1-100

10:10

10:10

0:10

2:10

10:10

10:10

10:10

0:10

0:10

10:10

0:10

10:10

10:10

3:10

10:10

0:10

10:10

10:10

10:10

0:10

0:10

10:10

10:10

5:10

0:10

0:10

10:10

8:10

<300

<5

8.6

59

.30

<5

<70

2.9

820

4.8

<20

7.1

1.3

43

<5

280

.037

2.0

<20

<2

44

2.28

1.56

2.19

1.41

1.62

2.47

2.56

1.45

1.59

1.56

2.23

5.99

2.42

1.7-45

24-140

.063-1.4

1.5-5.8

310-2,200

.79-29

1.1-47

.62-2.7

17-110

120-680

.0074-.18

.056-72

7.5-260

0:18

0:18

18:18

18:18

18:18

1:18

0:18

18:18

18:18

10:18

0:18

12:18

18:18

18:18

0:18

18:18

18:18

6:18

0:18

0:18

15:18

See footnotes at end of table.
18 GEOCHEMICAL ANOMALIES OF A CLAYPIT \REA.MISSOURI

TABLE 8. Mean chemical compositions, with central 95-percent range, of media that are comparable to those sampled in the

claypit area Continued

Element or compound

Al, or AlzOs, percent1............... .................. ...........

B ................................................................................

Ba . ........ . ...................... .

Be . .. .... .......... ..................................

Ca, or CaO, percent1 ..............................................

Cd .. .. ........... .. ... ................... ..

Ce .. . ........ .... ... .... ......

Co ..............................................................................

Cr ..............................................................................

Cu ..............................................................................

Fe, or total Fe as FeaOs, percent1 ......................

Ga ..............................................................................

Hg ..............................................................................

K, or K2O, percent1 ...............................................

La .............................................................................

Li ..............................................................................

Mg, or MgO, percent1 ............................................

Mo

Na, or NaaO, percent1 ..........................................

Nb ..............................................................................

Nd ... ... ..

Ni ..............................................................................

P, or ~PzOs, percent1 ................................................

Pb ..............................................................................

Sc ..............................................................................

Se ..............................................................................

Sr .............................................................................

V ........ ........... .. ........ .

Y ........................ ...

Yb .....

Zn .......................................... .. ....

Zr ......................... .............

Yellow sweetclover, total plant

GM

.................. 0.26

.................. 160

.................. 270

.................. <2

................. <300

.................. <5

.................. 4.6

............... 100

.................. .21

.................. <5

.................. <70

.................. 2.7

.................. 250

.................. 20

.................. <20

.................. 12

.................. .94

.................. 34

.................. <5

.................. 880

.................. .0091

.................. .82

.................. <20

.................. <2

.................. 1.8

GD

4.26

1.56

2.03

2.40

1.63

2.70

1.93

1.50

3.40

1.63

2.83

2.22

1.89

9 QQ

29.0

16.7

Central 95-

percent range

0.014-4.7

66-390

66-1,100

.80-26

38-270

.029-1.5

.72-10

110-560

1.7-230

4.5-32

.12-7.5

6.9-170

250-3,100

.0016 .052

.00098-690

.0065-500

Ratio

10:10

10:10

10:10

0:10

0:10

1:10

9:10

10:10

10:10

1:10

1:10

10:10

10:10

8:10

0:10

10:10

7:10

8:10

1:10

10:10

10:10

3:10

1:10

1:10

2:10

Parts of various species from throughout 

the conterminous United States

GM

0.65

240

390

<2

12

<300

.94

9.6

100

.36

.20

13

<70

3.0

1,000

4.2

.46

32

16

2.0

86

<5

880

A9C

ll

<20

<2

450

13

GD

3.52

2.10

3.75

2.69

5.83

2.85

1.98

2.51

9.83

1.82

2.05

A Qfi

3.94

4.00

6.21

2.84

2.27

6.17

3.78

3 49

4.15

2.73

3.44

Central 95-

percent range

0.052-8.1

54-1,100

28-5,500

1.7-87

....................

.028-32

1.2-78

26-390

.057-2.3

.0021-19

3.9-43

.71-13

57 21,000

.27-65

.029-7.4

.83-1,200

2.0-130

.39-10

2.3-3,300

62-13,000

.64-190

60-3,400

1.1-150

Ratio

1,109:1,117

1,133:1,150

1,151:1,151

8:1,153

988:988

2:1,117

232:1,119

1,096:1,139

1,153:1,153

1,153:1,153

150:1,105

1,006:1,006

46:1,123

1,120:1.153

1,153:1,153

453:1,124

277:277

. _ ..

11:47

1,028:1,135

991:991

980:1,142

39:1,153

1,145:1,152

1,122:1,148

694:1,123

158:1,128

101:1,108

642:643

470:1,152

'Means given for plants are percentages of the element; means for soils are percentages of the compound.

2Arithemtic mean.

'Standard deviation.

4Central 95-percent range is calculated as arithmetic mean minus two standard deviations to arithmetic mean plus two standard deviations.

One herd, composed of 54 older Angus cows on Ranch 

A, did not have access to the claypit area and in both 

1970 and 1971 it produced 54 live calves (table 5). A 

herd composed of 66 younger Angus cows that were 

pastured adjacent to the claypit area produced 31 live 

and five stillborn calves in 1970, and 23 live calves and 

one stillborn calf in 1971. A third herd, consisting of 

24 Charolais cows 4 years old, was kept on pastures 

unaffected by the claypit area, and in 1971 it produced 

24 live calves.

On Ranch B one yearling and four older Charolais 

bulls that had access to a pasture affected by runoff 

from the claypile developed the interference syndrome. 

These bulls were unthrifty, grew slowly, and gained 

weight at a very low rate, although they were on adequate rations for normal development. After being 

removed from the part of the pasture that was affected 

by runoff, the bulls slowly improved in condition, and 

finally recovered without obvious signs of permanent 

injury.

The yearling Charolais bull weighed approximately 

1,100 pounds (500 kg) when purchased in April 1970. 

During the following year he gained only 100 pounds 

(45.4 kg). On being returned to the southwestern Missouri ranch from which he came, he gained even more 

than the normal expected daily weight gain of 2-3 

pounds (0.9-1.4 kg). Using this latter rate of gain, it 

is estimated that a yearling Charolais bull could gain 

730 1,095 pounds (331.1 497.7 kg) in 365 days.

Herds 1 and 3 on Ranch A (table 5), which were not 

exposed to the pasture affected by runoff from the claypile, produced excellent calf crops, and the calves were 

normal and healthy. The breeding and calving record 

of Herd 2 which grazed on the affected pasture (table 

5) indicates that the interference syndrome greatly 

reduced the reproductive capability of the herd. In 

addition, the condition and growth rate of the cows 

were affected; in 1971 these cows averaged about 600 

pounds (270 kg) in weight, whereas normal Angus 

cows of the same age should weigh about 1,100 pounds 

(500 kg). After the 1971 calving season, all but 21 cows 

of this herd were disposed of, as it was apparent that 

they were not likely to reach the full size and weight 

usual for mature Angus cows. The calves produced by 

the 21 remaining cows were smaller and less growthy 

than is usual for Angus-Charolais calves.

Interference syndromes are slow to develop, and 

corrective response to a change in environment is likely
RESULTS AND DISCUSSION 19

TABLE 9. Concentrations of selected elements and compounds 

in anomalous amounts in one or more samples of clay from 

the claypit area, the average of these elements and compounds in soils in vicinity of the claypit, and the average 

for the Oak-Hickory Forest soil

[Values are in parts per million, except as indicated]

Element or 

compound |3 |§ 5rs;s 

|p |S «!.s!" o w -a

AlsOs, percent ......

Ba ............................

Be ............................

Ce ...........................

Co ............................

Cr ................ ...........

Cu ................... ........

Total Fe, as

FezOa, percent....

Ga ............................

KzO, percent .......

La ............................

Li ..........................

Mn .................... .....

Mo .................... . . .

Nd ..........................

Ni .. .. . ..

P2O5, percent ........

Sc ............................

Se ............................

SiO2, percent ........

Sr ............................

Ti, percent ............

V ..............................

Y ............................

Yb ..........................

30

500

3

300

7

300

70

2.2

50

3.6

jO

153

30

<3

150

100

.5

30

4

48

2,000

1

300

50

5

29

200

3

300

3

150

100

2

30

2.9

70

242

20

3

100

50

.5

30

3.2

45

700

.3

300

70

7

31

150

2

150

3

300

50

1.4

50

2.9

100

258

7

15

100

30

.3

30

1.7

44

700

.5

700

50

5

34

200

2

300

5

300

30

1.5

50

2.5

150

320

7

7

150

100

.2

50

3

46

700

1

700

70

7

33

30

2

<150

15

200

150

1

50

1.3

70

338

50

7

70

100

.1

30

.4

41

150

.5

500

20

3

8.4

700

<1

<150

13

65

12

2.8

14

1.8

54

22

810

<3

<70

14

.14

8.4

.4

76

160

.43

85

35

3.8

5.1

390

.77

78

10

43

13

2.7

8.4

1.3

35

18

730

<3

47

12

.076

5.4

.31

83

66

.35

53

27

2.8

1 Samples of clay from large pile east of claypit. Sample did not contain 

visible amounts of coal or sulfide minerals.

2 Sample of clay from smaller pile immediately north of large pile.

3 Sample of clay from southwest wall of claypit about 5 ft above water 

level.

4 Geometric means of 10 samples of soil (Nos. 22-31 of table 2) from the 

vicinity of the claypit. The samples were collected at depths of 2-15 cm and 

were not visibly contaminated with clay from the claypit.

5 Geometric means of 50 B-horizon soil samples from Oak-Hickory Forest 

areas in southern Missouri (Shacklette, Erdman, and Keith, 1971).

to be slow. The syndromes represented by the two 

groups of young cattle discussed in this report are not 

instances of calculated and controlled experimental 

procedures with known or predetermined factors. 

Although the cows in Herd 2 had free access to rations 

that were more than adequate for young beef cattle 

during their first gestation, their health steadily deteriorated, with malnutrition, loss of weight, signs of 

avitaminosis-A, and other evidence of starvation 

becoming apparent. Yet these interference phenomena 

were not fully appreciated for many months. Infectious 

diseases and other possible causes for the deterioration 

of the herd were ruled out insofar as was possible under 

the circumstances.

Although the history of the animals, and their condition as determined by observations, are of major 

importance in the establishment of a diagnosis, analyses from laboratory examinations provide very important supportive evidence and often reveal hidden interrelationships. The blood samples reported in tables 6 

and 7 were taken 8 months after the cattle had been 

removed from the affected pasture, and their analyses 

indicate a trend toward recovery of the animals. The 

trace element content of whole blood and the macromineral and enzyme values of the blood serum are

within the normal range for beef cattle, although the 

ratios of concentrations of some elements may be 

abnormal.

The effects of trace elements on human and animal 

health have recently been discussed by Selby, Marienfeld, and Pierce (1970). Deficiencies, as well as 

excesses, of certain elements may result in imbalances 

which disturb the normal nutrition and health of plants 

and animals (Mills, 1970; Church, 1971). The disturbance in animals may be so subtle as to suggest a minor 

ration deficiency, or so pronounced that an obvious 

toxicity is observed. We have worked with such interference phenomena before, and are of the opinion that 

the syndrome shown by the young cattle on both 

ranches discussed in this report is most likely a complex imbalance of molybdenum, cobalt, sulfate, and 

copper. Poole (1970) emphasized the fact that cytochrome oxidase activity is depressed by copper deficiency in the presence of interference by molybdenum or 

other trace substances. The copper values in blood 

shown in table 6 may be within low normal ranges, 

and are difficult to evaluate.

The severe depression of nutrition, growth, and 

reproduction in Herd 2 best fits a diagnosis of chronic 

molybdenosis as reported by Fleming, McCormick, and 

Dye (1961) from Nevada, and by Barshad (1948) from 

California. The changes in color and condition of the 

hair coat and the abnormal thickening of the skin also 

fit cases of unthrifty animals seen at our veterinary 

clinics during the last 20 years, and resemble those 

described by Muir (1941). Other workers have 

described similar metabolic disturbances from many 

places. (See Britton and Goss, 1946; Kretschmer and 

Beardsley, 1956; Underwood, 1970, 1971; Dye and 

O'Harra, 1959; Clarke and Clarke, 1967; Radeleff, 

1970; and Mills, 1970.)

Our diagnosis of the problem as an interference syndrome is supported by the studies of the element content of the vegetation and other materials from the 

area affected by drainage from the claypile, as given in 

tables 2, 3, 4, 9, and 10 of this report. Data in these 

tables suggest that in plants from the affected area, 

certain elements other than those linked to molybdenosis occur in concentrations greatly in excess of nutritional requirements of cattle, as well as above the usual 

ranges for such elements in Missouri plants (Pickett, 

1955; Church, 1971).

There could be many interrelations and imbalances 

of major and minor elements in addition to those mentioned. Several workers have reported imbalances in 

which phosphorus, calcium, or vital metabolic enzymes 

were adversely affected by anomalously high or low 

amounts of other substances ingested by cattle 

(Thompson and others, 1971; Britton and Goss, 1946;
20 GEOCHEMICAL ANOMALIES OF A CLAYPIT AREA. MISSOURI

Davis, 1950; and Muir, 1941). Nickel may contribute 

to interactions with other trace substances when present in excessive amounts, and may reach interference 

levels that correspond to the levels reported in tables 

2 and 3 (especially the levels in sweetclover and lespedeza). O'Dell and Miller (1971) discussed various 

aspects of nickel as it affects ruminant rations. Muir 

(1941) described the natural soil, pH, and related conditions which promote mineral imbalances such as 

anomalous concentrations of trace elements (especially 

molybdenum), and he cited the work of pioneers such 

as J. S. Watson who suspected the nature of the coppermolybdenum-sulfate and other trace element interrelationships early in the present century.

We are of the opinion that the young Charolais bulls 

on Ranch B farther down the valley were affected by 

the same trace element imbalances that caused the 

interference syndrome in Herd 2 of Ranch A. These 

bulls were not as near the sources of the environmental 

contamination as were the cows of Herd 2, and received 

less exposure to the water and vegetation that contained the anomalous concentrations of elements nearer 

the claypit. These bulls made better recovery of health 

than did the cows of Herd 2, when both were moved 

from the affected pastures.

The toxic plants native to the flood-plain pasture 

could make the imbalance of the trace elements worse, 

but has, in our opinion, made only minor contribution 

to the interference syndrome on Ranch A. The bulls on 

Ranch B were confined to lots where they did not have 

access to toxic plants, but grazed in a small pasture that 

was flooded by Rocky Branch, and they depended on 

a spring in the creek for their water supply. In our 

opinion, white snakeroot (Eupatorium rugosum) is the 

most dangerous of the toxic plants growing on either 

farm. Plants of the Nightshade Family, some of which 

are of known toxicity, are also present in the flood-plain 

pasture. We believe that the principal contribution of 

plants to the interference syndrome was not the organic 

poisons of certain plants, but the concentration of elements that were found in certain plants, especially 

sweetclover and lespedeza, that grew in the pastures. 

Buckbrush also is browsed by cattle, and it contained 

anomalous amounts of certain elements where it grew 

in the contaminated area. Direct ingestion of the clay 

and associated materials, or of water that carried these 

materials, may also have affected the metabolism of 

these animals.

SUMMARY AND CONCLUSIONS

Anomalous concentrations of elements in the claypit 

area were due, in a large measure, to the chemical composition of the materials that have been exposed by the 

mining operation. These materials include clay, shale,

coal, limestone, and pyrite. Pyrite is of special importance in effecting the release of certain elements into 

the natural environment because, by weathering, it 

produces sulfuric acid which is strongly reactive with 

other materials in the claypiles.

Water that drained from the claypiles into the claypit was highly acid and supported few aquatic organisms. We believe that the principal importance of the 

water in the local geochemical environment was its 

downstream transport of elements in solution and in 

particulate matter, and the subsequent deposition of 

these materials in the flood-plain alluvium and in the 

beds of the streams.

Plants that grow on the claypiles or in the alluvium 

that was carried from the claypiles may concentrate 

certain elements in their tissues as controlled by the 

inherent characteristics of the different species; and the 

concentrations present in the soil on which they grow. 

Some of these elements probably produce no important alteration of the natural environment, whereas 

others, if concentrated, are known to be toxic to most 

organisms.

In this summary, as in the report, element concentrations in the clay and in other materials brought to the 

surface by mining are regarded as anomalous wherever 

they differ from the range of concentrations to be 

expected in soils of the area.

Elements and compounds that are judged to occur 

in anomalous amounts in sampling materials from the 

claypit area are listed in table 10. Examination of this 

table reveals that the elements and compounds may be 

arranged in five groups, as follows:

1. Those that occur in anomalous amounts in the clay 

or alluvium, or both, and that also were found in 

anomalous amounts in many of the plant samples 

aluminum, copper, gallium, molybdenum, nickel, sodium, and ytterbium. Special mention should be 

made of cobalt, which is negatively anomalous in the 

clay but positively anomalous in five kinds of plant 

samples.

2. Those which occur in anomalous amounts in the clay 

and alluvium, but which were found in anomalous 

concentrations in none, or only a few, of the plant 

samples barium, beryllium, cerium, chromium, lanthanum, niobium, phosphorus, potassium, scandium, 

titanium, vanadium, and yttrium.

3. Those that occur in typical, or lower, concentrations 

in the clay and alluvium but, nevertheless, are absorbed in anomalous amounts by some plants 

boron, cadmium, calcium, and zinc.

4. Those which are anomalous in the clay or alluvium, 

but for which we have no means of evaluating their 

concentrations in plants carbon, lithium, neodymium, selenium, and silicon. Carbon is a major constit-
SUMMARY AND CONCLUSIONS 21

TABLE 10. Elements and compounds that occur in anomalous concentrations in one or more samples of materials from

the claypit area.

[+, anomalously high; °, typical; , anomalously low; ........... no data available]

Materials sampled

Element or compound

Al, or A12OS ...................................................

B ...................................................................

Ba .................................................................

Be .................................................................

C, total .........................................................

C, organic .....................................................

Ca, or CaO ...................................................

Cd .................................................................

Ce .................................................................

Co ................................................................

Cr ...................................................................

Cu .................................................................

Fe, or total Fe

as Fe2Os .

Ga

K, or K2O .....................................................

La .................................................................

Li ...................................................................

Mg, or MgO .................................................

Mn .................................................................

Mo .................................................................

Na, or Na2O .................................................

Nb .................................................................

Nd .................................................................

Ni .................................................................

P, or P2O« .....................................................

Pb .................................................................

Sc ...................................................................

Se ...................................................................

Si, or SiO2 .....................................................

Sr ...................................................................

Ti ...................................................................

V ...................................................................

Y ...................................................................

Yb .................................................................

Zn .................................................................

Clay from ««. __, JRBS. "^

+ +

0 0

 o

+ +

 o

o +

0 0

o o

+ +

 o

+ +

+ +

 o

+ +

+ +

+ +

+ +

o o

 

+ +

 o

o +

+ +

+ +

+ +

o +

+ +

+ +

_ _

+ +

+ o

+ +

+ +

+ +

o o

White oak 

stems

+

o

-

o

-

+

o

+

o

+

o

o

+

+

0

o

+

-

o

+

o

o

o

o

o

o

o

+

+

Buckbrush

stems

+

o

o

0

o

+

o

0

o

+

+

+

0

o

+

-

o

+

o

o

o

o

+

o

o

o

Smooth 

sumac 

stems

o

o

o

o

o

+

o

+

o

o

0

o

o

o

+

o

+

-

o

o

o

o

o

o

o

o

o

o

o

Redcedar 

stems and 

leaves

+

o

-

+

o

o

o

+

+

+

o

+

o

o

-

o

o

-

o

+

o

o

+

-

+

+

o

+

o

Grasses 

and sedge, 

aboveground 

parts1

+

+

o

o

o

+

+

o

+

+

o

o

o

o

o

o

o

o

o

o

+

o

0

+

White 

sweetclover, 

total plant

+

+

o

o

o

+

+

+

o

+

o

o

+

+

o

+

o

+

o

o

+

o

o

o

Other 

forbs, 

aboveground 

parts8

0

o

o

o

o

o

o

o

+

o

o

o

o

o

o

o

o

o

+

o

o

o

o

o

o

o

+

o

1Bluegrass, common bullrush, fowl meadow grass, Japanese chess, meadow fescue, red top, timothy, and wood reed grass. 

2Cattail, common plantain, goldenrod, Japanese clover, and white snakeroot.

uent of plants; the other elements are nonessential to 

plant metabolism.

5. Those whose tendencies in concentrations and movements through the local environment cannot be 

readily categorized with the data that are now available iron, lead, magnesum, manganese, and strontium.

Elements in groups 1 and 3 potentially can influence 

the metabolism of grazing animals because of their concentrations in plants, or their presence in deposits of 

the clay on the plant surfaces. Elements in groups 1 

and 2 can affect these animals if the clay or alluvium 

is ingested directly, or if water is drunk in which these 

elements are in solution or suspension, even if the vegetation is not grazed.

Plants that concentrate certain elements in high 

amounts may be particularly important in contributing 

to nutritional disorders of animals, especially (as in 

sweetclover and Japanese clover) if the plants are very 

palatable and therefore preferentially grazed. The importance to the geochemical environment of certain less

palatable accumulator plants, such as the trees and 

shrubs sampled in this study, may lie principally in 

their ability to concentrate certain elements in the 

upper soil horizons where they are readily available to 

other plants.

In evaluating the total geochemical environment of 

the claypit area, four elements (beryllium, copper, 

molybdenum, and nickel) are seen to be conspicuously 

anomaldus in the clay, alluvium, and plant samples. 

Moreover, the mobilities of certain elements (aluminum, beryllium, cobalt, copper, and nickel, among 

others) are demonstrated by their high concentrations 

in efflorescent salts and in the claypit water. Cobalt, 

although not anomalous in the clay and alluvium 

samples^ is a common anomaly in the plant samples. Of 

these elements, cobalt, copper, and molybdenum are 

known to be metabolically significant; in trace amounts 

they are essential to animals, but in high concentrations may be toxic. Aluminum occurs in anomalously 

high concentrations in all sampling media, and in an 

acid environment such as may be provided by the oxida-
22 GEOCHEMICAL ANOMALIES OF A CLAYPIT AREA, MISSOURI

tion of pyrite it is readily mobile. However, high concentrations of aluminum were found in plants only in 

samples that were on or near the claypiles. If highly 

concentrated, aluminum is thought to be toxic to 

animals.

The interpretation of the movements of elements 

and compounds through the local environment from 

their principal source to grazing animals is summarized in figure 3.

The interference with normal growth, nutrition, and 

reproduction in the cattle was caused by the severe 

imbalance of several elements that occur in anomalous 

concentrations in both the drainage from the claypit 

area, and in the vegetation contaminated by this drainage The most likely imbalance is in the complex relationship between copper and molybdenum, which is 

possibly influenced by other elements that are present 

in anomalous concentrations and that can, in themselves, influence metabolism of cattle. Similar interference syndromes (or toxicities) in which young cattle 

are most seriously affected are known to occur in the 

States of California, Florida, and Nevada, and in Canada, Europe, Australia, and other places.

In field situations, some variables of the animals' 

actual feed intake are not measurable the amount of 

any one plant that the animals eat, whether all animals 

eat the same plants, the season of plant growth, and 

the individual consumption of feed supplements. Unlike 

laboratory experiments, the natural environment cannot be treated as a rigorously controlled system. Therefore, diagnosis of metabolic disorders must employ 

plausible inferences that are supported by observations 

of the animals, study of the laboratory results, and 

evaluation of the total environment to which the animals were subjected.

The clay and associated materials that were exposed 

by the clay mining operation contain concentrations of 

certain elements that can be considered anomalous in 

the natural geochemical environment of plants and animals. Runoff from the claypiles transports these elements, either in solution or in suspended sediment, to 

other parts of the area. These elements generally can 

be absorbed by plants, and some of them may be concentrated to high levels. Of the elements studied, aluminum, beryllium, cobalt, copper, molybdenum, and 

nickel generally were found to have the greatest mobil92° 02' 30"

38° 

37' 

30"

7 X>j r\

CLAYPILES - SOURCE OF THE ELEMENTS THAT 

MOVE IN ANOMALOUS CONCENTRATIONS INTO 

THE STREAMS, ALLUVIUM, AND CLAYPIT WATER

Aquatic organisms in claypit 

water killed by acid or element content, or both

Certain elements, through chemical reactions and movement, are made 

available to grazing animals in:

1. Water and water-clay mix in intermittent streams and ephemeral 

pools in the streambeds

2. Clay deposited on plant parts during flooding

3. All parts of plants that grow on the flood plain and concentrate 

""? certain elements

Oxidation of pyrite forms sulfuric acid which increases 

solubility of certain compounds in the clay pile

Element-concentrating plants grow on and around the 

claypiles; when these plants decay, the elements are 

released in a readily mobile form

Elements in participate and soluble form are trans- -i 

ported downslope by runoff j)

) Dilution of soluble elements in runoff.^^^^^^, ( _ 

( f Some elements, in both soluble form v^X

and particulate matter, can be concen--x ^^^^^ 

trated by plants growing on the flood ^^ VJ) Plai" " ' ^.

s~ ' .Ranch B D

Particulate and soluble 

elements carried 

downstream

1000

I

2000

i

3000 FEET

__I

FIGURE 3. Movement of elements through the geochemical system, claypit area, Callaway County, Mo.
REFERENCES CITED 23

ity in the local environment and to occur most commonly in anomalous concentrations through the area.

Young beef cattle exposed to anomalous element 

concentrations in the flood plain below the claypile 

experienced a severe interference syndrome due to an 

imbalance of minerals or other nutrients in their feed 

or water, or both. The disturbance in metabolism of 

cattle grazing on pastures affected by the claypile was 

most similar to chronic molybdenosis. Imbalances of 

copper and molybdenum, in addition to those of sulfate, nickel, cobalt, and other substances, may have 

contributed to this syndrome.

Anomalous concentrations of elements that present 

a hazard to livestock may exist at many other locations 

in Missouri and throughout the Midwest where similar 

materials are brought to the surface by clay and coal 

mining, especially if the chemical mobility of elements 

is increased under the acid conditions that may result 

from the presence of pyrite.

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24 GEOCHEMICAL ANOMALIES OF A CLAYPIT AREA, MISSOURI

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U.S. GOVERNMENT PRINTING OFFICE: 1973 515 6S8/SO