COVER: Design by Sunne Rinkus, 1990. 
Proceedings of a U.S. Geological Survey 

Workshop on Environmental Geochemistry 

Edited by BRUCE R. DOE 

U.S. GEOLOGICAL SURVEY CIRCULAR 1033 
U.S. DEPARTMENT OF THE INTERIOR 

MANUEL LUJAN, Jr., Secretary 

U.S. GEOLOGICAL SURVEY 

Dallas L. Peck, Director 

Use of trade, product, or firm names in this publication is for descriptive 

purposes only and does not imply endorsement by the U.S. Government 

UNITED STATES GOVERNMENT PRINTING OFFICE: 1990 

Free on application to the 

Books and Open-File Reports Section 

U.S. Geological Survey 

Federal Center, Box 25425 

Denver, CO 80225 

Library of Congress Cataloging in Publication Data 

U.S. Geological Survey Workshop on Environmental Geochemistry (1986 : 

Reston, Va.) 

Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry I edited by Bruce R. Doe. 

p. em. - (U.S. Geological Survey circular ; 1033-C) 

Bibliography: p. 

Supt. of Docs. no.: I 19.4/2;1033 

1. Environmental geochemistry-Congresses. 2. Environmental geochemistry-United States-Congresses. I. Doe, Bruce R. II. Geological Survey (U.S.) Ill. Title. IV. Series. 

QE514.4.U22 1966 

551.9-dc20 90-600181 

CIP 
PREFACE 

Environmental geochemistry encompasses both natural chemical (geochemical) hazards and anthropogenic environmental concerns. For example, the household radon 

contamination that generated so much public awareness in 

1986 can be considered a natural radiochemical hazard 

except in those cases involving mine tailings from uranium 

and phosphate deposits. The radon emanates through natural processes dependent upon the abundance of radioactive 

parents of radon (most significantly 238U and 326Ra) and the 

permeability of the rock or soil upon which a house is built. 

On the other hand, the effects of chemical waste disposal 

(for .example, dioxin) are an anthropogenically induced 

concern. Some contamination problems can be extremely 

complex and involve a combination of both natural and 

anthropogenic causes. The selenium problem at the Kesterson Reservoir in the western San Joaquin Valley of California, for example, seems to involve concentration of 

naturally occurring selenium as a result of irrigation practices. The quality of our drinking water also depends on 

both natural and anthropogenic factors. 

When an environmental geochemical problem arises, 

the public expects a rapid response from scientists and 

organizations. To help prepare for possible future concerns, 

the U.S. Geological Survey held a workshop in April 1986 

to determine what sorts of studies have been completed or 

are in progress and to generate some ideas regarding future 

studies. This circular summarizes the proceedings of that 

workshop and provides a sampling of the kinds of investigations the U.S. Geological Survey is prepared to do. This 

circular is not an exhaustive compendium. For those desiring greater detail, reference can be made to publications 

listed in the bibliography by Shacklette and colleagues (this 

volume). 

The U.S. Geological Survey often can quickly reorder priorities to encompass newly recognized societal concerns. In the case of environmental geochemistry, two 

examples of rapid reprogramming are discussed in included 

papers and are briefly described here. Gundersen (this 

volume) was conducting field-geochemical uraniumresource studies in the Reading Prong of Pennsylvania, 

New York, and New Jersey when the household radon issue 

surfaced in the now famous Watras house early in 1985. 

She was able to rapidly alter her course of mapping from 

emphasis on uranium resource to radon environmental 

geochemistry. In another example, when the selenium 

concern arose at the Kesterson Reservoir in California 

(overview by Sylvester, this volume), Tidball and colleagues (this volume) were able to draw on a suite of 

samples previously collected and analyzed for reconnaissance mineral-resource evaluation and low-density geochemical mapping purposes. Because of the reconnaissance 

nature of the original study, the simple, rapid analytical 

technique used was not extremely precise and did not 

measure selenium, arsenic, and mercury. Therefore, Tidball and colleagues reanalyzed the samples by more precise 

means and added the toxic elements to the suite. This 

reanalysis enabled them to rapidly develop the soil traceelement distribution maps that identify the area in the 

· vicinity of the Panoche-Cantus Creek fans in western 

Fresno County as being the selenium-enriched source area 

(described more fully by Presser (this volume)). A more 

thorough discussion of selenium in the West is given by 

McNeal and colleagues. Soils are especially important in 

environmental geochemistry investigations, and so thorough attention is given to them (for example, papers by 

Tidball, by Pavich, and by McNeal), as well as to various 

aspects of bedrocks (papers by Conner, by Hearn and 

colleagues, by Orem, and by Kotra). 

Concerns involve not only toxic levels of elements 

and compounds but also deficiencies of essential elements. 

Selenium, for example, is needed in human and animal 

diets. Indeed, in the eastern San Joaquin Valley, some 

fields are doped with selenium to provide grazing animals 

with adequate amounts of this element in their diets. The 

diet of most Americans is sufficiently varied so that getting 

adequate selenium is not an issue. Plant geochemistry, in 

general, plays a major role in environmental studies, 

however, beyond providing nutritional information and thus 

is broadly discussed herein (by Erdman, by Milton, and by 

Gough and colleagues). 

The techniques used in environmental geochemistry 

are not confined to chemical analyses or geologic field 

mapping. Duval (this volume) applies aerial gamma-ray 

data gathered by the U.S. Department of Energy's National 

Uranium Resource Evaluation Program (NURE) to the 

household radon issue. Thus, this investigation uses data 

gathered for a purpose not originally intended, as in the case 

of the San Joaquin Valley. 214Bi is a decay product of 222Rn 

in the radioactive decay chain of 238U and is the radioisotope actually measured; thus the NURE data are directly 

applied to radon concerns. Several papers explore the 

applicability of other geophysical techniques to environmental geochemistry (for example, papers by Frischknecht 

and by Clark and King). Various kinds of electrical property 

Preface Ill 
measurements appear to be particularly appropriate (papers 

by Olhoeft and by Bisdorf). Unique properties of asbestos 

varieties require detailed mineralogical studies (paper by 

Ross). Stable and radioactive isotopes also have considerable application (papers by Spiker and by Muhs and 

colleagues, respectively). 

Perhaps most,if not all, of the Nation's estuaries are 

suffering from pollution effects. (Examples of concerns in 

Massachusetts are given in two papers by Bothner and 

another by Butman.) Subsurface problems associated with 

estuaries are discussed by Helley, and Butman discusses 

offshore aspects. Manheim discusses some possible consequences of submarine mining. 

Although this circular gives an impressive sampling 

of efforts and capabilities of the U.S. Geological Survey in 

environmental geochemistry, it is by no means comprehensive. Only the most timely topics are emphasized herein. 

Unaddressed are issues relating to major elements that pose 

potential hazards, such as aluminum and magnesium, and 

numerous minor elements (for example, arsenic, barium, 

IV Preface 

cadmium, lead, mercury, and zinc). It is also recognized in 

light of the experience at the Kesterson Reservoir, Calif., 

where samples collected for resource purposes allowed 

rapid response to an environmental concern, that data 

collected for purposes of resource exploration geochemistry 

can have considerable application to future environmental 

concerns. Society's concern over environmental geochemistry does not seem to abate. Each year seems to bring a new 

issue. In spite of this happening, only one State, Missouri, 

has complete coverage of environmental data in even a 

preliminary fashion (see papers by Shacklette, by Miesch, 

and by Erdman and letter by Howe). Organization within 

the U.S. Geological Survey to address these problems 

seems appropriate. A first step was the initiation of the 

Toxic Substances Hydrology Program (see Mallard and 

Ragone, this volume). Initial planning on a possible program involving solid materials has been outlined by Filipek. 

Consideration is being given to a comprehensive overall 

plan. 

Bruce R. Doe 

Assistant Director for Research 

U.S. Geological Survey 
CONTENTS 

Preface, by Bruce R. Doe III 

NATIONAL OVERVIEWS 

1. Environmental Geochemistry Program, by Lorraine H. Filipek 1 

2. Toxic substances hydrology-Surface- and ground-water contamination, by Gail 

E. Mallard and Stephen E. Ragone 7 

3. The state of soil and plant geochemical surveys, by Hansford T. Shacklette 11 

4. Geochemical studies-The Missouri experience, by A.T. Miesch 21 

5. Written communication on environmental geochemistry in Missouri, to Bruce 

Doe, by Wallace B. Howe 25 

TOPICAL STUDIES 

Soil and stream-sediment geochemistry 

6. Soil studies in the northern Great Plains, by Ronald R. Tidball 27 

7. Weathering process research-Pedology and soil geochemistry in drainage basins, 

by Milan J. Pavich 33 

8. The mode of occurrence of extractable elements in soils from the northern Great 

Plains, by James M. McNeal 37 

9. Uranium-series disequilibrium in Quaternary soils-Significance for 222Rn hazard 

assessment, by Daniel R. Muhs, Charles A. Bush, and John N. Rosholt 39 

Plants 

10. Biogeochemical baselines and the importance of species, plant parts, and 

season-The U.S. Geological Survey's studies of big sagebrush in the West, by 

James A. Erdman 45 

11. Vegetation studies in the northern Great Plains, by Larry P. Gough 47 

12. Remote sensing of vegetative responses to the environment, by Nancy Milton 51 

13. Cooperative studies by the U.S. Geological Survey and the U.S. National Park 

Service in environmental biogeochemistry, by Larry P. Gough, R.C. Severson, 

and Larry L. Jackson 53 

Geochemistry and mineralogy of reservoir rocks 

14. Monitoring geochemical processes with geophysics, by Gary R. Olhoeft 57 

15. Bedrock geochemistry and the environment, by Jon J. Connor 61 

16. Geochemistry of rock-water reactions in basalt aquifers of the Columbia River 

Plateau, by Paul P. Hearn, Jr., William C. Steinkampf, Lloyd D. White, and 

John R. Evans 63 

17. Early diagenesis and metal-organic matter interactions in alkaline playa lakes of 

the Lahontan basin, Nevada, by W.H. Orem 69 

18. The role of organic matter in weathering processes, by R.K. Kotra 71 

Regional geophysics and geochemistry 

19. Application of geophysical methods to the study of pollution associated with abandoned and injection wells, by Frank C. Frischknecht 73 

20. The use of spectroscopy in environmental geochemical studies, by Roger N. Clark 

and Trude V. V. King 79 

Contents V 
VI Contents 

21. Application of stable-isotope techniques to environmental geochemistry, by Elliott 

C. Spiker 83 

Regional geology 

22. Quaternary geology and pollution problems-An example from the San Francisco 

Bay area, California, by Ed Helley 87 

23. Toward a capability for predicting transport of sediments on the continental shelf 

and slope and in submarine canyons along the northeast coast of the United 

States, by Bradford Butman 97 

Natural resources and anthropogenic concerns 

24. Characteristics of coal-mine wastes for rehabilitation work, by 

R.C. Severson 103 

25. The role of coal characterization in the control of acid precipitation, by Jack H. 

Medlin and Frederick 0. Simon 105 

GEOLOGY, GEOPHYSICS, AND GEOCHEMISTRY OF SITES 

San Joaquin Valley, California 

26. Overview of the salt and agricultural drainage problem in the western San Joaquin 

Valley, California, by Marc A. Sylvester 119 

27. A potential source area for selenium and mercury in agricultural drainage water at 

Kesterson Reservoir, San Joaquin Valley, California, by Ronald R. Tidball, R.C. 

Severson, James M. McNeal, and Stephen A. Wilson 125 

28. Geoelectrical studies of the Panache fan area of the San Joaquin Valley, 

California, by Robert J. Bisdorf 133 

29. Initial shallow seismic tests in the Panache fan area, Fresno County, California, 

by Wilfred P. Hasbrouck 139 

30. Relation of selenium at Kesterson National Wildlife Refuge to potential soilforming source rocks, by T.S. Presser 143 

Massachusetts harbors 

31. Heavy-metal accumulations in sediments of Boston Harbor, Massachusetts, by 

Michael H. Bothner 145 

32. New Bedford Harbor and Buzzards Bay-Transport of pollutants on fine-grained 

marine sediments, by Bradford Butman 149 

33. The Georges Bank monitoring program-Trace metals in bottom sediments, by 

Michael H. Bothner 155 

Beluga coal field, Alaska 

34. Geochemical studies of plants and soils in the Beluga coal field, Alaska, by R.C. 

Severson and Larry P. Gough 159 

North Carolina phosphate 

35. Potential saltwater intrusion into freshwater aquifers during exploration for 

and mining of phosphorite off the Southeastern United States, by Frank T. 

Manheim 161 

SPECIAL PROBLEMS 

Radon 

36. Some basic facts about radioactive radon, by Joseph S. Duval and Allan B. 

Tanner 163 

37. Geology of the Reading Prong, New York, and its application to predicting areas 

that have high radon potential, by Linda C. Gundersen 165 
38. The role of National Uranium Resource Evaluation aerial gamma-ray data in 

assessment of radon hazard potential, by Joseph S. Duval 169 

39. Potential for indoor radon hazards-A first geologic estimate, by James K. 

Otton 171 

Toxic particulates 

40. Hazards associated with fibrous minerals, by Malcolm Ross 175 

Selenium 

41. Environmental concerns related to selenium in the Western United States, by 

James M. McNeal, Gerald L. Feder, William G. Wilber, and Stephen J. Deverel 

177 

Copper-molybdenum 

42. Copper-molybdenum imbalances and the incidence of nutritional diseases in livestock and humans, by James A. Erdman 179 

BIBLIOGRAPHY 

43. Bibliography of selected geochemical studies of the environment by the U.S. Geological Survey, compiled by Hansford T. Shacklette, R.C. Severson, and Larry P. 

Gough 183 

FIGURES 

2.1. 

3.1-3.6. 

6.1. 

6.2. 

6.3. 

6.4. 

6.5. 

7.1. 

9.1. 

9.2-9.4. 

Map showing location of U.S. Geological Survey hydrologic studies of 

toxic substances 8 

Maps showing examples of: 

3. 1. A regional geochemical study using various sampling 

materials 12 

3.2. A regional geochemical study of soils and plants encompassing the 

entire conterminous United States 13 

3.3. A regional geochemical study that includes only one type of sampling 

material 14 

3.4. A regional geochemical study in which airborne chemical elements in 

plants are sampled 15 

3. 5. A geochemical survey of areas having political boundariesMissouri 16 

3.6. A geochemical survey of areas having political boundariesAlaska 17 

Map showing location of the northern Great Plains coal region 27 

Illustrations of hypothetical element distributions along traverses where the 

regional variation is absent or present, northern Great Plains 28 

Flowchart for choice of optimum method of data display 29 

Examples of data presentation of significant variance components 30 

Diagrammatic representation of a barbell design 31 

Generalized soil map of the conterminous United States 34 

Diagram of the upper part of the 238U-series decay chain 39 

Graphs showing: 

9.2. Category 1 disequilibrium in the Berino soil from Eddy County, N. 

Mex. 40 

9.3. Category 2 disequilibrium in soil from the Nevada Test Site 41 

9.4. Category 3 disequilibrium in soil from southern New Mexico and 

Barbados 42 

11.1. Map showing sampling locations within the area of strippable coal deposits, northern Great Plains 48 

Contents VII 
VIII Contents 

12.1. 

12.2. 

13.1. 

14.1. 

14.2. 

15.1. 

16.1. 

16.2. 

l6.3. 

16.4. 

17.1. 

19.1. 

19.2. 

19.3. 

20.1. 

20.2. 

20.3. 

22.1. 

22.2. 

22.3-24.1. 

Plot showing spectral reflectance measurements of greenhouse-grown red 

maple and loblolly pine trees 52 

Plot showing spectral refectance curves of NiS04 -stressed and control 

hosta plants and first derivative spectra 52 

Map showing past and present national park and recreation units 

investigated under the U.S. Geological Survey-National Park Service 

Cooperative Environmental Biogeochemistry project 54 

Complex resistivity spectra of clay soil from Henderson, Nev., 

uncontaminated and contaminated with organic waste from an industrial 

site 58 

Complex resistivity spectra of clay soil from Willow Springs, La., 

uncontaminated and contaminated with organic waste from a leaking 

landfill 59 

Diagram showing the role of rocks in influencing the near-surface geochemical environment 61 

Map of study area in the Columbia River Plateau showing location of 

water wells and sampling sites for secondary minerals 64 

Molar plot of dissolved sodium, calcium, and magnesium 

concentrations in ground water, grouped in terms of relative age, Columbia River Plateau 65 

Graph showing average concentrations of dissolved silicon, potassium, 

dissolved oxygen, and pH, plotted in terms of relative ground-water age, 

Columbia River Plateau 66 

Graph showing formation temperatures computed by using in-situ &180 

values 67 

Elemental data and 13C nuclear magnetic resonance spectrum of 

dissolved organic matter isolated from an alkaline playa lake 70 

Aeromagnetic contour map over part of Coon Creek oil field northeast of 

Oklahoma City, Okla. 75 

Locality map showing electromagnetic soundings and test drill holes near 

Pawhuska, Okla. 76 

Electrical sections interpreted from electromagnetic soundings near 

Pawhuska, Okla. 76 

Near-infrared reflectance spectra of powdered chrysotile, lizardite, and 

antigorite 80 

Near-infrared reflectance spectra of powdered tremolite and 

actinolite 81 

Near-infrared spectra of a sodium montmorillonite and calcium 

montmorillonite 82 

Aerial photograph of Silicon Valley, Calif., 1959 88 

Aerial photograph of Silicon Valley, Calif., 1977 89 

Maps showing: 

22.3. Alluvial deposits related to geological processes in the Palo Alto 

area, California 90 

22.4. Soil units in the Palo Alto area, California 92 

22.5. Distribution of younger and older alluvial deposits in the Palo Alto 

area, California 94 

22.6. Surficial geology of the Palo Alto area, California 95 

23. 1. Location of instruments deployed on the continental shelf between 

1975 and 1982; in and around Lydonia and 

Oceanographer Canyons from 1980 to 1982; and on the outer shelf 

and slope between 1982 and 1984 97 

23.2 Tidal currents and mean currents on Georges Bank, Nantucket 

Shoals, and the southern New England shelf 100 
25.1. 

25.2. 

25.3. 

25.4. 

25.5. 

25.6-25.8. 

25.9. 

26.1. 

26.2. 

26.3. 

26.4. 

26.5. 

26.6. 

27.1. 

27.2-27.5. 

24.1. General location of coal surface mines sampled in the Western 

United States 103 

Sketch showing link between resource identification, mining, and coal 

preparation and pollution emissions and the fate of acidic compunds in the 

atmosphere 106 

Sketch showing coal-quality parameters important in coal 

utilization 107 

Map showing coal basins of the continental United States 110 

Diagram showing total sulfur versus demonstrated reserve base of coal in 

the United States 111 

Outline of the Pittsburgh coal bed showing sample locations 112 

Diagrams showing: 

25.6. Variability of sulfur and ash within a mine in an eastern coal 

field 113 

25.7. Standard procedures in coal preparation 114 

25.8. Nitrogen dioxide and sulfur dioxide concentration in U.S. 

coal 116 

Graph illustrating impact of changing the present compliance standard on 

Kentucky's coal resources 117 

Map showing location and main features of study area, western San Joaquin Valley, Calif. 120 

Map showing main water distribution and drainage systems and wetlands 

in the study area, San Joaquin Valley, Calif. 121 

Conceptual model of sulfur and selenium mobilization and 

transport 122 

Diagram of climate, irrigation, and drainage in the western San Joaquin 

Valley, Calif. 122 

Cross-sectional sketch of western San Joaquin Valley showing location of 

clay layers and major aquifers 122 

Map showing selenium concentrations in surface and ground water of the 

western San Joaquin Valley from Tracy to Kettleman City, 

Calif. 123 

Map showing San Luis Drain Service Area and Panoche fan study area, 

San Joaquin Valley, Calif. 125 

Maps showing the distribution of: 

27 .2. Selenium at 0- to 12-in. soil depth in the San Joaquin Valley, 

Calif. 127 

27 .3. Mercury at 0- to 12-in. soil depth in the San Joaquin Valley, 

Calif. 128 

27 .4. Selenium at 66- to 72-in. soil depth in the Panoche-Cantua Creek 

fan area, San Luis Drain Service Area, Calif. 129 

27.5. Mercury at 66- to 72-in. soil depth in the Panoche-Cantua Creek fan 

area, San Luis Drain Service Area, Calif. 130 

28. 1. Map showing the location and identifying number of the Schlumberger 

soundings, Panoche fan area, California 134 

28.2. Two typical Schlumberger sounding curves, Panoche fan area, 

California 134 

28.3-28.5. Contour maps of interpreted resistivity, Panoche fan area, California: 

28.3. At a depth of 5 m 135 

28.4. At a depth of 10 m 136 

28.5. At a depth of 20m 138 

29. 1. Three radial-source/radial-seismometer, shear-wave, spot-test seismograms 

from seismic site 1, Panoche fan area, California 139 

29.2. Three radial-source/radial-seismometer, shear-wave, spot-test grams from 

seismic site 3, Panoche fan area, California 140 

Contents IX 
X Contents 

29.3. 

31.1. 

31.2. 

31.3. 

32.1. 

32.2. 

32.3. 

33.1. 

33.2. 

33.3. 

33.4. 

33.5. 

34.1. 

35.1. 

35.2. 

36.1. 

36.2. 

37.1. 

37.2. 

38.1. 

38.2. 

38.3. 

42.1. 

43.1-43.4. 

Radial-source/radial seismometer, shear-wave, combined-trace, commonmidpoint section at seismic site 1, Panoche fan area, 

California 141 

Diagram showing relative concentrations of metal in digested sewage 

sludge from Boston's treatment plant, average concentration in the upper 2 

em of sediment, concentration in average crustal rocks, and concentration 

in clay collected 2 m below sediment surface in Boston Harbor, 

Mass. 146 

Profiles of metal concentration plotted against sediment depth in a core 

collected from Hingham Bay in Boston Harbor, Mass. 147 

Profile of 137 Cs activity plotted against sediment depth in a core 

collected from Hingham Bay, Boston Harbor~ fallout record for 137 Cs 

measured in New York City between 1954 and 1978; and profile of excess 210Pb plotted against sediment depth, Mass. 147 

Map of Buzzards Bay, Mass., showing locations where current or nearbottom sediment movement observations have been made 150 

Photograph showing bottom tripod system designed for studies of nearbottom sediment transport 151 

Graphs indicating suspended sediment concentration in New Bedford, 

Mass. , November 1-December 21 , 1984 152 

Map showing regional sampling array, Georges Bank 156 

Diagram showing site-specific sampling station array around regional station 5 (block 312), Georges Bank 156 

Diagrams showing concentration of barium in bulk sediment near the drill 

site at block 312, Georges Bank 157 

Graph showing total inventory of barite within the 0.5- to 2-km annulus 

around station 5, Georges Bank 157 

Graph showing decrease of the net barite inventory within the 0.5- to 2-

km annulus around station 5, Georges Bank, with time 158 

Map showing location of the Capps coal field, Alaska 159 

Map showing location of hydrochemical transect B-B' from Georgia to the 

Blake Plateau 161 

Hydrochemical transect B-B' from Georgia to the Blake Plateau 162 

Diagram showing 238U decay series 163 

Diagram showing common paths of entry of radon into homes 164 

Map showing location of magnetite and uranium deposits in the 

Reading Prong 166 

Graph plotting uranium and iron versus metamorphic rock type in the 

Reading Prong, New York and New Jersey 167 

Diagram showing a portion of 238U decay series 169 

Graph showing surface area measured as a function of the height of the 

detector 169 

Graph showing percentage of surface area covered versus the flight-line 

spacing 170 

Photograph showing a group of young men having deformity of the knee 

joint resulting from high dietary intake of molybdenum 181 

Maps showing: 

43. 1. Geochemical studies of the broadest scale in the conterminous 

United States 184 

43.2. Geochemical studies of the broadest scale in Alaska 186 

43.3. Locations of numbered regional geochemical studies of rocks, 

stream sediments, soils, plants, and waters 187 

43.4. Locations of numbered geochemical studies of rocks, soils, plantsthe effects of pollution and relation to human and animal nutrition 

and disease 191 
TABLES 

6. 1. Terrain mean and baseline for mercury in soil samples of each terrain when 

the difference between terrains is significant but the difference within terrains 

is not significant 30 

6.2. Grand mean and baseline for boron in soil samples of entire study area when 

the difference between terrains is not significant 30 

8.1. The relative order of importance of factors for all extractable 

elements 38 

15 .1. Estimates of expected metal concentration in shale 62 

16.1. Compositional variation during paragt!nesis 64 

17 .1. Organic-matter composition of Carson Lake sediments 69 

17 .2. Major- and minor-element composition of Carson Lake sediments 70 

25.1. Data items for the U.S. Geological Survey National Coal Resources Data 

System's USCHEM data base 108 

25.2. Quantities of trace elements mobilized as a result of coal 

production 110 

25.3. Minerals known to occur naturally in coal 115 

25 .4. Relation between sulfur and depositional environment in the Donetz basin, 

U.S.S.R. 116 

34.1. Observed range in concentration of six elements in samples of two soil zones 

and three plant species from the Capps coal field, Alaska 160 

42.1. Breeding and calving history of three distinct beef-cattle herds on Ranch A 

for the 1970 and 1971 breeding and calving seasons 180 

Contents XI 

1. Environmental Geochemistry Program 

By Lorraine H. Filipek 

INTRODUCTION 

Issues and Problems 

Taken collectively, environmental issues have 

become one of the most visible concerns of the American 

public for several decades. Every few months a new 

environmental problem surfaces. High selenium concentrations at the Kesterson Reservoir in the San Joaquin Valley 

are causing death and deformities in wildlife. Acid rain is 

degrading water quality in eastern lakes. Indoor radon 

pollution may increase risk of lung cancer and is being 

discovered in new areas daily, including major population 

centers like Washington, D.C., and Philadelphia. Soil 

erosion is seriously reducing the amount and quality of our 

Nation's and the world's topsoil. 

The combined cost of these problems is tremendous 

in terms of both dollars and quality of life. For example, the 

Federal Government has already spent several million 

dollars trying to correct the Kesterson selenium problem, 

and the Office of Technology Assessment recently estimated that it could cost as much as $100 billion to clean up 

the more than 10,000 hazardous waste sites that pose a 

serious threat to public health (Magnuson, 1985). Remedial 

actions such as these are orders of magnitude more expensive than prior scientific assessment and proper preventive 

measures. The Committee on Irrigation-Induced Water 

Quality Problems of the National Research Council (NRC) 

pointed out in its review (Eliot, 1985, p. 921) of the Bureau 

of Reclamation's San Joaquin Valley Drainage Program, 

"Failure to assess the problem explicitly in advance wastes 

time and multiplies effort. This appears to be happening to 

a degree in the San Joaquin drainage (selenium) studies." 

The San Joaquin study was singled out by the NRC, but the 

statement applies in general to environmental problems 

because there is no systematic environmental assessment 

strategy in the United States. Moreover, no such strategy 

can exist until we have a better understanding of the 

surficial Earth. 

Manuscript approved for publication April 6, 1989. 

The Earth functions as an interactive system of land, 

water, air, and biota. Physical, chemical, and biological 

processes occurring at and near the Earth's surface are 

important in all of the previously mentioned environmental 

issues. Naturally occurring selenium, weathered from 

nearby mountains, is transported to soils and concentrated 

in drainage water from crop irrigation in the west side of the 

San Joaquin Valley. The effects of acid rain depend upon 

the ability of the local soils and rocks to neutralize the 

acidity. The radon gas invading homes is a natural product 

of the radioactive decay of uranium and is concentrated 

through complex interplay among bedrock, soils, the atmosphere, and house construction. Rates of agricultureinduced soil erosion depend on the local geomorphology. 

It is becoming increasingly evident that we live in an 

environment that has important, but generally poorly 

known, broad-scale variations. In a manner similar to 

regional topographic variations, geochemical processes and 

concentrations show important regional differences. The 

natural causes of some of these variations are at least 

partially understood. For example, the mobility of anionic 

species such as selenium, arsenic, uranium, and boron is 

much higher in the alkaline, saline soils and waters of the 

arid Western United States than in the acidic soils of much 

of the humid East, whereas cations such as lead, zinc, 

cadmium, and iron are more mobile in acidic environments. 

For the most part, however, the causes and extent of 

regional variations and the resulting variable impact of 

human activities are not clear. 

The U.S. Geological Survey (USGS) has several 

programs that provide much needed data on regional water 

quality and hydrology. But water is only one component of 

the surficial Earth system. The quality of surface and 

ground water is a function of the geochemistry and geomorphology of the land-the sediments, soils, and rocks-over 

and through which the water moves. The land plays several 

roles. It may act as a "filter" or sink, stripping water of 

human and natural contaminants; as a natural source of 

contamination due to high concentrations of potentially 

toxic elements associated with mineral deposits; or first as 

sink and then as source responding to changes in human 

activities, such as building or draining a reservoir. The 

actual earth materials themselves, eroding at accelerated 

Environmental Geochemistry Program 1 
rates due to human activities, cause surface-water quality 

problems due to their sheer volume. 

Thus, to determine which natural and human factors 

control our surficial environment, we must understand the 

interactions among land, water, air, and biota. However, 

present information is limited on both ( 1) the concentrations 

of naturally occurring toxic or nutrient elements in the soils 

and rocks of the highly complex and variable natural 

geologic environment and (2) the types and rates of processes involved in the redistribution of elements and surficial materials under different geologic and climatic regimes 

(weathering and erosion). Problem-specific programs such 

as those related to acid rain or toxic wastes have been 

funded to investigate various individual environmental 

issues. However, there is as yet no truly integrated approach 

to the study of the surficial-Earth system. Geologic, 

geochemical, and geophysical data on earth materials and 

weathering-process studies that span the climatic and geologic extremes of the Nation are needed to develop systematic environmental assessment and mitigation strategies. 

Such strategies are needed if we are to recognize and 

effectively solve present and unforeseen environmental 

problems, or better yet, to prevent them from arising at all. 

The timing for the Environmental Geochemistry Program is right. We have not only the need, but also the 

technical and knowledge base to make great progress in 

understanding the various surficial processes and incorporating that understanding into effective strategies to protect 

the Earth from irreversible degradation. With the Environmental Geochemistry Program, geochemical data and 

process-related information on bedrock and erosion products will be collected to provide the framework for understanding and interpreting the physical, chemical, and biological characteristics of the land-surface environment. In 

addition, the understanding gained about the functioning of 

the surficial Earth will be incorporated into systematic 

environmental assessment strategies to protect our Nation's 

and the Earth's environmental health. 

Justification for U.S. Geological Survey Action 

The USGS was established as a scientific agency to 

provide information about the Earth for use in reaching 

informed decisions related to national needs. The quality of 

the environment is one of the most important and publicized 

national and international concerns of our time. It is also 

one that invokes extremely emotional debate. The issues 

involved are scientifically complex, and there is inadequate 

understanding of the causes and of the effectiveness of the 

proposed solutions. The cost of environmental problems in 

lawsuits alone is immense, not to mention the cost of 

cleanup or mitigation, which in many cases is inadequate or 

ineffective. The USGS is national in scope and has a 

reputation for being an impartial scientific agency responsible for information on earth-science issues. Therefore, 

data and assessments presented by the USGS are likely to be 

viewed as objective by all interested parties. 

The USGS is investigating the quantity and quality of 

the Nation's wat~rs, with topographic and geographic 

information system (GIS) input and coordination with other 

agencies. These efforts will constitute the Nation's first 

fully integrated investigation of the surficial Earth environment. The complementary USGS Environmental Geochemistry Program is needed to ( 1) compile existing geoscience 

data and build new data bases about the materials that make 

up the land surface, including concentrations of rockforming, toxic, and nutrient elements and their relation to 

geologic and geomorphic features; (2) gain an understanding of weathering and erosion processes affecting the 

chemical and physical makeup of these surficial materials; 

and (3) integrate the data bases and process-oriented 

research into coherent strategies to assess the environmental 

quality of the Nation. 

Collection of geochemical and geomorphic data on 

solid earth materials and investigation of the physical, 

chemical, and biological processes occurring at and near the 

land surface are necessary to provide appropriate mitigation 

strategies to reduce present environmental contamination or 

degradation (or know when mitigation is ·unfeasible given 

the geologic constraints). Further, development by the 

USGS of systematic assessment strategies will allow rapid 

determination by Federal and State agencies of areas that 

have the greatest present and potential contamination or 

degradation hazards and will allow development of appropriate land-use strategies to prevent further health hazards 

and (or) environmental deterioration. Finally, this program 

will provide an effective, efficient medium for cooperative 

interaction by the USGS with other international, Federal, 

and State agencies, universities, and scientific organizations 

who are interested in particular environmental problems. 

PROGRAM DESCRIPTION 

Objective 

The program objective is to develop an integrated 

multidisciplinary, or "interdisciplinary," framework within 

which broad-scale environmental problems can be 

addressed. This framework will include: 

1. Development of a national data base of environmental 

geochemistry and surficial-Earth parameters that 

includes concentrations of rock-forming, toxic, and 

nutrient elements and their relation to geologic, geomorphic, hydrologic, biologic, climatic, and present landuse variables. 

2. Research leading to a more quantitative understanding of 

the physics, chemistry, and biology of weathering and 

erosion processes and the rates of these processes on 

spatial scales ranging from molecular to regional and 

global. 

2 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
3. Development of optimum environmental assessment 

strategies and reports in cooperation with other appropriate agencies, focusing first on areas of known immediate risk to health and the environment. 

4. Systematic production of scientific reports and of 

regional and national environmental assessment maps. 

Anticipated Benefits of the Program 

The anticipated benefits of the program include the 

following: 

1. Evaluation and prediction of areas having environmental 

contamination or degradation hazards and ability to 

distinguish between the effects of natural processes and 

human activities. 

2. Establishment of geochemical baselines for solid earth 

materials against which potential future changes can be 

assessed. 

3. Scientifically based mitigation strategies for reducing 

contamination and degradation of surficial-Earth materials. 

4. Greatly decreased financial and health costs from environmental hazards. 

STRATEGY 

General Description 

We propose to develop an integrated multidisciplinary framework that will allow a systematic assessment 

of present and potential environmental quality and the 

factors that control that quality. The Environmental 

Geochemistry Program will collect geochemical data and 

process-related information, drawing heavily upon relevant 

data bases and experiences of previous work. The Environmental Geochemistry Program will be closely coordinated 

with the National Geologic Mapping, Climate, National 

Mineral Resource Appraisal, Development of Assessment 

Techniques, Acid Rain, Toxic Substances Hydrology, 

Radioactive Waste, and other relevant USGS programs. 

The combined research and assessment map products of the 

Environmental Geochemistry, Climate, and other USGS 

programs will allow Congress; international, Federal, and 

State agencies; and individuals to develop appropriate 

strategies to reduce present environmental contamination 

and degradation and to minimize future problems. 

The strategy of the Environmental Geochemistry 

Program is ( 1) to investigate broad-scale environmental 

problems in specific geographic areas (study areas) of 

various sizes in cooperation with other agencies, (2) to use 

an integrated multidisciplinary approach that draws upon 

the full arsenal of relevant USGS expertise, and (3) to 

extrapolate the resultant information to better understand 

issues at the regional, national, and global level. Investigations that will be carried out in this program are of two 

complementary types: 

Environment-oriented. -Comprehensive investigations within a single environment, such as determination of 

the influence of different parent rock types on weathering 

rates and chemical composition of weathering products 

within a particular ecoregion and calculation of average 

regional weathering rates. (An ecoregion is a region having 

relatively uniform factors that cause and integrate surficial 

environmental processes, including climate, physiography, 

potential natural vegetation, soils, and land use (Omemik, 

1987, p. 118-125).) This type of investigation has value on 

several scales. It is useful in isolating areas within the 

ecoregion that have present or potential environmental 

problems due to local geochemistry, such as the selenium 

problem in parts of the San Joaquin Valley, Calif., due to 

high concentrations of naturally occurring selenium in the 

soils and ground water of the Panoche Fan. It also provides 

necessary regional geochemical baseline information for 

monitoring the effects over time of such broad-scale processes as acid rain and regional or global changes in 

temperature or ozone. 

Issue-oriented. -Statewide and nationwide investigations of a single issue, such as the geologic and geochemical 

causes of high indoor radon levels in houses, lead or arsenic 

in soils and drinking water, nitrates in ground water, or 

cadmium in crops. This type of investigation will incorporate surveys and research at several small study areas in 

different geologic and climatic settings across the Nation. It 

will allow rapid national evaluation and prediction of areas 

having the greatest potential for acute problems. 

The environment-oriented and issue-oriented investigations will provide valuable transfer of information to each 

other in an iterative manner. The priorities for study-area 

selection will be based on knowledge of potential natural 

contamination or degradation hazards, on the perceived 

need for a rapid response, and on the interest and cooperation of other Federal and State agencies. Highest priority 

will be given to those regions or problems on which several 

agencies are able to work cooperatively. The study areas 

will be the focus of activities of the program's five 

elements: 

1. Data management and analysis to determine the availability and quality of existing surficial-Earth data and to 

integrate the data into a standard format suitable for a 

national data base of environmental geochemistry and 

surficial-Earth parameters. 

2. Geochemical and geophysical surveys to identify and 

distinguish between present anthropogenic toxicelement sources and natural sources, such as bedrock, 

mineralization, and weathering products, and to quantify 

the degree of natural chemical input to the surficial 

environment. 

Environmental Geochemistry Program 3 
3. Interdisciplinary field and laboratory weathering-process 

research to identify the factors that affect the types and 

rates of rock-water and rock-air interactions at Earthsurface conditions and to determine transport rates and 

mechanisms. 

4. Methodology research to develop approaches and analytical methods as required to meet other programmatic 

objectives. 

5. Environmental assessment mapping, based on systematic assessment strategies, to allow rapid determination 

of those areas having the highest present and potential 

contamination or degradation risks. 

Development of the assessment strategy for each 

environmental problem will be iterative over the generally 

4- to 7-year course of a study-area project. In the first and 

second years, existing data will be compiled, and a set of 

hypotheses and a preliminary assessment map will be 

developed. Beginning in the second year and continuing 2 

to 5 years, geophysical and geochemical surveys and 

weathering-process research will be conducted in the study 

area. 

In the final year of field research, the survey and 

research information will be synthesized into a summary 

report and a revised environmental assessment map for the 

area. Generalizations of contamination or degradation processes will be developed on the basis of the new information 

gained in the study areas, and regional, national, and 

international assessment maps will be developed as appropriate. 

Program Elements 

Data Management and Analysis 

Many studies have already been done on various 

aspects of the surficial Earth. This information is scattered 

throughout the literature and at various Federal and State 

agencies, universities, and private repositories. Before any 

field work is started at a particular study area, the relevant 

existing data will be assembled, organized, and put into a 

standard format suitable for a national data base of environmental geochemistry and surficial-Earth parameters. 

Study-area maps will be compiled of geology, topography, 

soil properties, geophysical features, vegetation, hydrology, and land use, by using GIS technology. When applicable, a statistically determined subset of National Uranium 

Resource Evaluation (NURE) stream sediment samples will 

be analyzed statistically or reanalyzed chemically for elements of interest. For radon, aeroradiometric geophysical 

maps derived from the NURE data base will be generated. 

Geological maps will be compiled cooperatively by the 

USGS and the relevant State survey, usually as part of the 

National Geologic Mapping Program. The USGS will 

compile hydrologic maps that have been developed through 

its various programs. The other maps will be developed 

cooperatively by the USGS and other appropriate agencies. 

The final products will be prepared by the USGS. 

Geochemical and Geophysical Surveys 

The geochemical and geophysical surveys will provide new baseline data on the materials that make up the 

surface and near-surface environment. Together with the 

maps prepared in the first program element, they will 

provide the context within which the process-oriented field 

work will be accomplished. 

Geochemical surveys will focus on the production of 

statistically stable (reproducible) geochemical maps and 

data bases for each element of interest in each geochemical 

medium appropriate to the study area, including soil, rock, 

stream sediment, surface and (or) ground water, and vegetation. These baseline data are important because they 

indicate what is '"normal" in any particular area and provide 

the background context within which problems can be 

identified. Geochemical maps have already proven 

extremely useful in identifying potential problem areas, 

such as the source area for the elevated selenium concentrations at the Kesterson Reservoir in the San Joaquin 

Valley. Existing geochemical information generally will be 

compiled for the study area in the year preceding initiation 

of the geochemical survey to aid in selection of the most 

appropriate sample media. The actual sampling scheme will 

be designed to suit the needs of the particular study area. 

Before the onset of the first survey, a quality-assurance 

program and quality-control procedures will be instituted 

for the collection, preservation, storage, and analysis of all 

samples. 

Geophysical surveys will focus on development of 

the physical framework of the surface and subsurface using 

remote-sensing techniques. Broad-scale satellite and airborne surveys will provide the regional framework, and 

detailed ground-based surveys will outline specific problem 

areas. Spectral techniques will be used to map vegetation 

and areas of vegetation stress. Various electrical, electromagnetic, seismic, and radar techniques will be used to map 

stratigraphy, water table, aquifer boundaries, rainfall wetting fronts, and contaminant plumes, where appropriate. 

Weathering Process Research 

Weathering process research will be designed to gain 

a quantitative understanding of the types and rates of 

interaction among surficial-Earth parameters, such as bedrock geology and geochemistry, geomorphology, soil properties, biology, hydrology, climate, and land use, and the 

sensitivity of these interactions to change. Integration of an 

understanding of modem processes with knowledge of the 

Quaternary geologic record will allow effective use of the 

geologic record to determine the relation between frequency 

and magnitude of geologic events and to establish a predictive capability. The focus of research will vary with the 

4 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
particular study area, but the approach will always be 

interdisciplinary, with synthesis of the results that will 

allow extrapolations to similar situations elsewhere in a 

national and global context. The understanding gained will 

enable international, Federal, and State agencies and individuals to develop effective, scientifically based mitigation 

strategies to combat contamination or degradation problems. Four major activities will be carried out in this 

element. 

1. Detailed investigations of rock, soil, water, plant, 

and microbe interactions for different lithologies within a 

single ecoregion or geomorphic unit to determine (a) the 

effect of different rock chemistries on rates of weathering 

and erosion within an area of relatively uniform external 

environmental variables, (b) the effect of geomorphology 

on the types and rates of weathering of the parent rock and 

erosion of the associated soil, (c) the geochemical forms of 

the major and trace elements in the soils and waters from 

selected sites within the study areas, and (d) the causeand-effect relations of geochemistry and geomorphology to 

the plant and soil-microbe communities. The mineralogy, 

geochemistry, and paragenesis of the soils will be determined. Biological research will aim at a better characterization of the relation between biota and the geochemistry 

of the associated soils. 

2. Investigations of the geochemistry and transport 

of naturally occurring source materials to determine the 

contribution of natural systems to toxic and radioactive 

elements in surface and ground water and soil gas, where 

applicable. These studies will allow separation of natural 

and anthropogenic sources and will aid in determining the 

feasibility of various mitigation strategies. The objective of 

this research will be to determine the geochemistry and 

transport of toxic elements in and around a range of 

mineralized systems and problem source rocks in the study 

areas or similar environments elsewhere. Research will 

include the determination of (a) the geochemical processes 

active at the rock-water or rock-air interface; (b) the effects 

of climate, geomorphology, and bedrock geology on the 

rates of toxic-element weathering and transport; (c) the 

geochemical and physical changes that occur to the soil and 

rock as they are transported to and enter the stream 

environment; (d) the seasonal variations in soils, stream 

sediments, and waters; and (e) the ultimate sinks for the 

toxic elements. 

3. Investigations of organic-inorganic interactions to 

determine the nature and extent of toxic inorganic element 

associations with organic compounds in the surficial and 

near-surface environment. Studies will be both field and 

laboratory oriented. They will include investigations of (a) 

the effects of environmental variables such as Eh (oxidation 

potential) and pH on the ability of organic compounds to 

sorb trace elements, (b) the effect of organic sorption onto 

inorganic particles, such as clays and oxides, on the 

particle's cation exchange capacity and ability to sorb trace 

elements, and (c) the effects of degradation of organic 

contaminants on the mobility of toxic inorganics. 

4. Investigations of the geochronology of weathering 

processes to determine temporal variations in process rates 

and to assess the effects of past Quaternary climates on the 

rates and types of soil formation. Evidence suggests that 

soil formation in some environments is a series of stepfunctions rather than a continuous process. However, our 

knowledge of the thresholds that trigger change is very 

limited. This knowledge is essential to understanding the 

consequences of soil degradation and processes of soil 

formation and regeneration. A major aspect of this activity 

will be the use of Quaternary dating techniques to correlate 

synchronous events and calibrate time sequences. 

Methodology Research 

The research will consist of developing and improving techniques of geochemical, geophysical, biological, and 

computer analysis needed to carry out the goals of the 

program. The research on geochemical analysis will focus 

on ( 1) the development of new techniques to investigate the 

surface properties of solid-earth materials; (2) the identification and quantification of the complex chemical forms of 

oxide-forming and toxic elements in the surficial environment; (3) the development of fast, inexpensive, and accurate techniques for the determination of trace concentrations 

of naturally occurring toxic elements in solid-earth materials; and (4) the development and improvement of techniques used for concentrating trace elements in water and 

soil extracts. A critical requirement for surface-property 

investigations is the purchase of a major piece of analytical 

instrumentation with which to "see" the surface layer, such 

as an X-ray photoelectron spectrophotometer or an Auger 

electron spectrophotometer. 

Geophysical research will be conducted to refine 

indirect detection and measurement techniques, such as 

electrical techniques for detection of contaminant plumes 

and processes, and other remote-sensing techniques for 

identifying such features as stressed vegetation and mineral 

distributions. Biological research will aim at better determination of "indicator" plants and microbes used as chemical monitors of stressed soil environments. The research on 

computer analysis will address the GIS technology that will 

be used to manipulate, integrate, and analyze the large data 

sets created and also will focus on such problems as 

correcting for the inconsistencies of NURE aeroradiometric 

data. 

Environmental Assessment Mapping 

Efforts will focus on ( 1) statistical determination of 

the relations among elements and between element concentrations and geology, geomorphology, ecoregion zone, soil 

properties, biology, hydrology, and land use; (2) development of environmental assessment strategies based on 

Environmental Geochemistry Program 5 
integration of the statistical interrelations and the processoriented research; and (3) systematic production of study 

area, regional, and national environmental assessment maps 

of surficial-earth materials. 

The preliminary regional or national assessment map 

for any particular toxic element will be formulated on the 

basis of existing geochemical data and information about 

mineral deposit districts, geology, ecoregion zone, hydrology, and land use. A scoring technique will be developed 

similar to that used in mineral-resource assessment. 

Research in computer analysis technology and expert systems will guide formulation of later environmental assessment maps. 

REFERENCES CITED 

Eliot, Marshall, 1985, San Joaquin flooded with water researchers 

(news and comment): Science, v. 230, no. 4728, 

p. 920-921. 

Omemik, J.M., 1987, Ecoregions of the conterminous United 

States: Annals of the Association of American Geographers, v. 77, no. 1, p. 118-125. 

Magnuson, Ed, 1985, A problem that cannot be buried: Time 

Magazine, v. 126, no. 15, p. 76-84. 

6 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
2. Toxic Substances Hydrology-Surface- and 

Ground-Water Contamination 

By Gail E. Mallard and Stephen E. Ragone 

INTRODUCTION 

Contamination of the Nation's ground and surface 

waters by toxic wastes is considered by many to be one of 

the most significant environmental issues of the decade. 

Billions of gallons of contaminated liquids are discharged 

into the environment each year (Miller, 1980), and virtually 

all States have some ground- and surface-water problems 

resulting from toxic organic chemicals or heavy metals 

(U.S. Geological Survey, 1984). The extent of the problem, 

with regard to the percentage of ground water and surface 

water affected, is not clearly defined. However, problems 

such as those encountered at Love Canal, N.Y., have 

focused public attention on the extensive social and economic impact that can result from even a relatively small 

area of ground-water contamination. As with ground-water 

contamination, awareness of the seriousness of surfacewater and sediment contamination by hazardous substances 

has increased dramatically in recent years. Conditions such 

as the occurrence of dioxins at Times Beach, Mo., kepone 

in the lower James River, Va., and polychlorinated biphenyls (PCB's) in the Hudson River, N.Y., sediment and 

water have received widespread attention from Federal, 

State, and local agencies and the general public. 

Successful implementation of laws and regulations to 

reduce environmental degradation from toxic waste contamination requires earth-sciences information. The U.S. Geological Survey's (USGS) Toxic Substances Hydrology Program fulfills an important role in identifying the extent of 

these problems and providing earth-sciences information 

needed to improve waste-disposal practices and to help 

mitigate existing and future surface- and ground-water 

contamination problems. The program supports studies to 

( 1) develop new and refine existing methods of sampling 

and measuring hazardous substances in ground and surface 

waters, aquifer and sediment materials, and biota and (2) 

acquire a greater understanding of the biological, physical, 

geological, and chemical processes and other factors that 

affect hazardous substances in ground- and surface-water 

systems. This information is necessary to appraise the 

occurrence, movement, and fate of hazardous substances in 

the Nation's ground and surface waters and sediments and 

to determine how these are changing with time. 

The program has three major goals: (1) to pursue a 

broad range of fundamental process-oriented research and 

methods-development efforts related to contamination of 

both surface and subsurface hydrologic systems; (2) to 

conduct intensive, interdisciplinary field researc.h of specific surface and ground waters contaminated by selected 

types of chemicals; and (3) to improve methods for collecting, analyzing, and interpreting hydrochemical information 

at regional scales to determine the extent and magnitude of 

contamination. Studies conducted in the program can be 

divided into three areas-process-oriented research and 

methods development, focused field investigations and 

research, and supportive regional investigations. 

PROCESS-ORIENTED RESEARCH AND 

METHODS DEVELOPMENT 

This component of the program includes research in 

the following topical areas: 

Ground-water hydrology. -Research is being conducted to provide a quantitative understanding of the flow 

of water and the transport of its constituents through the 

subsurface. New mathematical methods are being developed to better explain the mechanisms by which contaminants mix with ground water or are transported through rock 

fractures and how gaseous or nonwater phase fluids move 

through the ground. 

Erosion and sediment transport. -Many of the toxic 

substances that are found in rivers are attached to, and 

transported with, sediment. Conceptual and mathematical 

models are being adapted or developed to describe the cycle 

of detachment, movement, and deposition of sediments in 

river basins. 

Inorganic and organic geochemistry. -The movement of inorganic and organic contaminants may be 

affected by a variety of reversible or irreversible chemical 

reactions such as ion exchange, mineral solution or precipitation, ion filtration, absorption or desorption, oxidation or 

Toxic Substances Hydrology-Surface- and Ground-Water Contamination 7 
-------- G I -r----

asotine I : -------- • : ~ ---~---------:---'1 I J~ ' I ..... ...,... ... . ' \ I I .. _,.._ "-----..______ 1 ..., 'Crude 

---) s' II \ Oil •• <..'l l • I 

( i. :-------------) ·" 

/ ~v-. .. rf·----------1 Whitewood Creek-Belle'? 

------ : J ~~Fourche! River ~... .... '-. 

7-- I I I I ' 

I

I ---.:... ____ .,...__ i .----------...... r·--------~,. I I -; I' .. -... ..,.\ ~----

i : L__ I ~ ) I 

\

. 1 ;---------'--- • High Plail)s 1 \ ' u . I l (~--------~ I •sa· PPer Arkan I r' _________ :\ \ i 

"\Joaqu· ! sas River 1 , ?"' \_ ~ 

'Valley ,, i I o• II oe High Plains I I / ...!'..( " .J~ ', ,_._____ I I : .. ,... ,.,...... ,, '"' _....---------- \ _J ---i----____ Arkansas River Valley 1-S -------~--T---. \~ I -,c:::.:.=;-·--------~---------;.J ___ ....-· Fracture5\ Rock 

\ : : . \ ... ? f ...,.,.---'---, > Metals 1 1 I i { -----r--..... · ,.. II , : . r----,.- , ' ( : • i '"" ! j ! \ -,..._ -- . I Albuq ·--.., ' ;s • ' ...,. ~- , uerque-Belen ~""'~ ..... ---"' ... .!.., { I \ ·. '·· !' Basin! r··----'? : > .. 8 nol 

'· J' • • \" I ' p tachloroP•• '-...t..r·-&\·--·--- ~ ~\~- . l creosote/ e~ 

EXPLANATION "· ·1\.~Calcacreu \ - ----\..------~~h ·"\ Edwards Aquifer ~~ RTver"1. H·· .... -~ • • (.i -STREAM REACH, SURFACE-WATER QUALITY ~.. ,~·-··, • f\O idBR Aquifer 

• REGIONAL GROUND·WATER QUALITY STUDIES '-. • \ 

'\ 

\ .. ...... 

• RESEARCH SITES, GROUND-WATER QUALITY 

0 INTENSIVE STUDIES, FY 87 , 

Figure 2.1. Location of U.S. Geological Survey hydrologic studies of toxic substances. 

reduction, complexation, and degassing. Research is being 

conducted to characterize ( 1) the trace inorganic and 

organic species found in surface and ground water and (2) 

the pathways, rates, and controlling factors or reactions of 

important trace contaminants. 

Ecology.-Living organisms accumulate and alter 

inorganic and organic trace substances. Studies are being 

conducted to quantitatively relate the concentrations of 

toxic substances in water and sediment to the concentrations 

of toxic substances in aquatic biota. 

Methods development. -Major research and development are underway to improve methods for sample collection, sample preparation, and analysis for toxic substances. 

Efforts are being directed toward devising better techniques 

to obtain representative samples of ground water contaminated by organic chemicals, improving methods for extracting both metals and organic chemicals from solids, and 

improving the ability to detect and quantify substances 

present at extremely low concentrations. 

FOCUSED FIELD INVESTIGATIONS AND 

RESEARCH 

Field investigations conducted in the Toxic Substances Hydrology Program provide the opportunity to 

bring together process-oriented and methods-development 

research in the study of the fate and transport of important 

types of organic and inorganic contaminants in ground- and 

surface-water systems (fig. 2.1). In addition to forming a 

better understanding of earth-sciences processes, the studies 

allow for the development of new study approaches that can 

be applied to subsequent studies conducted in the FederalState Cooperative Program or in other Federally funded 

programs. 

Five interdisciplinary field studies (squares on fig. 

2.1) are being conducted to characterize the physical, 

chemical, and biological processes affecting the fate and 

transport of trace metals and manmade organic substances 

in the subsurface. In fiscal year (FY) 1983, studies began at 

sites where ground-water contamination resulted from a 

crude-oil pipeline break near Bemidji, Minn., the infiltration of creosote and pentachlorophenol from waste-disposal 

pits near Pensacola, Fla., and the infiltration of sewagetreatment effluent on Cape Cod, Mass. 

Reports describing the studies have been published 

(Hult, 1984; Mattraw and Franks, 1984; LeBlanc, 1984; 

and Franks, 1987). In FY 1985, additional sites were 

selected to study ground-water contamination resulting 

from chlorinated hydrocarbons at Picatinny Arsenal, N.J., 

and an acid-contamination plume in Arizona. 

Interdisciplinary river-basin investigations are being 

conducted to describe the occurrence of hazardous 

8 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
substances in water, sediment, and biota and to characterize 

the fundamental processes that affect these substances in 

surface waters. Three intensive river-basin investigations 

(begun in FY 1985 and 1986) are underway and focus on ( 1) 

organic chemicals from industrial effluent that is discharged 

into the Calcasieu River in Louisiana, (2) mine wastes 

containing high concentrations of arsenic and trace metals 

that were discharged into the Whitewood Creek and the 

Belle Fourche River system in South Dakota, and (3) water 

flowing into the Upper Arkansas River in Colorado from 

mine drains and abandoned tailings that contributes large 

amounts of cadmium, copper, iron, and other metals. 

SUPPORTIVE REGIONAL INVESTIGATIONS 

In FY 1984, the USGS began reconnaissance-phase 

studies in 14 States (circles on fig. 2.1) in an attempt to test 

procedures that would systematically evaluate the extent of 

ground-water contamination. A detailed description of the 

approach used in the studies has been published (Helsel and 

Ragone, 1984). Briefly, the objectives of the studies are to 

systematically collect and use hydrogeologic, land-use, and 

water-quality data to ( 1) provide information on ambient 

ground-water chemistry with emphasis on organic substances and trace metals to explain the chemistry in terms of 

the local hydrology and human activities and (2) identify the 

causes, effects, and processes that are applicable to similar 

areas elsewhere. Study areas range in size from a few 

hectares to a few thousand square kilometers. Regardless of 

the scale, each area is characterized by relatively uniform 

climatic and geohydrologic conditions. The general hydrology and ground-water flow system in the study area are 

reasonably well understood, and a reasonable body of data 

is available on inorganic chemical quality of ground water 

and land use. 

The reconnaissance phase of the 14 assessments of 

ground-water quality in major geohydrologic regions of the 

Nation was completed in FY 1985. Of the 14 areas 

(diamonds on fig. 2.1), six were selected for more intensive 

study. 

REFERENCES CITED 

Franks, B.J., ed., 1987, U.S. Geological Survey Program on 

Toxic Waste -Ground-Water Contamination-Proceedings of the Third Technical Meeting, Pensacola, Florida, 

March 23-27, 1987: U.S. Geological Survey Open-File 

Report 87-109, 193 p. 

Helsel, D.R., and Ragone, S.E., 1984, Evaluation of regional 

ground-water quality in relation to land use; U.S. Geological Survey Toxic Waste-Ground-Water Contamination 

Program: U.S. Geological Survey Water Resources Investigations Report 84-4217, 33 p. 

Hult, M.F., ed., 1984, Ground-water contamination by crude oil 

at the Bemidji, Minnesota, research site; U.S. Geological 

Survey Toxic Waste-Ground-Water Contamination Program: U.S. Geological Survey Water Resources Investigations Report 84-4188, 107 p. 

LeBlanc, D.R., ed., 1984, Movement and fate of solutes in a 

plume of sewage-contaminated ground water, Cape Cod, 

Massachusetts; U.S. Geological Survey Toxic WasteGround-Water Contamination Program: U.S. Geological 

Survey Open-File Report 84-0475, 180 p. 

Mattraw, H.C., Jr., and Franks, B.J., eds., 1984, Movement and 

fate of creosote waste in ground water, Pensacola, Florida; 

U.S. Geological Survey Toxic Waste-Ground-Water 

Contamination Program: U.S. Geological Survey OpenFile Report 84-0466, 93 p. 

Miller, D. W., 1980, Waste disposal effects on ground water: 

Berkeley, Calif., Premier Press, 512 p. 

U.S. Geological Survey, 1984, National water summary, 

1983-Hydrologic events and issues: U.S. Geological Survey Water-Supply Paper 2250, 243 p. 

Toxic Substances Hydrology-Surface- and Ground-Water Contamination 9 

3. The State of Soil and Plant Geochemical Surveys 

By Hansford T. Shacklette 

The application of soil and plant geochemistry to 

environmental studies requires data on "normal" values in 

element concentrations to assess changes that have occurred 

or to predict changes that may occur in the geochemical 

environment. Data for certain types of natural materials, 

available from many published reports, may facilitate the 

planning and execution of a proposed study by providing 

baseline values for identifying anomalous values in the 

sampling media. If baseline data are not available, they 

must be established in the course of the proposed environmental study, thus increasing the cost in time and money for 

completing the project. It is appropriate, therefore, to 

review the present state of soil and plant geochemical 

studies, including available data bases for many elements, 

before planning future environmental studies. 

The data bases already established differ in the 

objectives for which the data were developed, the chemical 

elements considered, and the geographical areas studied. 

For example, for geochemical studies focused on exploration for mineral deposits, only a few chemical elements 

were analyzed, and the study areas usually were small. 

These data may be of limited application to some kinds of 

geochemical studies, or they may be very useful in solving 

specific environmental problems. Other geochemical studies were centered on specific problems of environmental 

contamination or on establishing baselines for normal element concentrations in soils and plants or other natural 

objects. These environmental studies may be separated into 

two types: (l) topical studies such as point-source emissions 

(Miesch and Huffman, 1972) and mine-spoil reclamation 

(Gough and Severson, 1981) and (2) regional studies having 

as their objective the characterization of geochemical landscapes, often using multimedia sampling, as was done in 

the study of the western energy region summarized by 

Ebens and Shacklette (1982) (fig. 3.1) in which geochemical characteristics were evaluated for various sampling 

materials by, among others, Schultz and others (1980) 

(rocks); McNeal (1982) (stream sediments); Severson and 

Tidball (1982) (soils); Erdman and Gough (1982) (plants); 

and Feder (l982a) (waters). Other regional studies were of 

soils and plants of the conterminous United States (Shacklette and Boerngen, 1984) (fig. 3.2). 

Multielement geochemical studies that are based on 

smaller geographic scales may include only one type of 

sampling material, such as big sagebrush in eight western 

physiographic provinces (Gough and Erdman, 1982) (fig. 

3.3) and airborne chemical elements in plants (Shacklette 

and Connor, 1973; Connor and Shacklette, 1984) (fig. 3.4). 

Studies at smaller scales may also include many kinds of 

sampling materials (rocks, residuum, loess, native and 

cultivated plants, uncultivated and cultivated soils, waters, 

and so on) from separate locations in the conterminous 

United States (data summarized in Connor and Shacklette, 

1975). Another type of multielement geochemical study 

may consider only a sampling material of direct economic 

value, such as the geochemical characterization of fruits and 

vegetables and their supporting soils from major areas of 

commercial production (Shacklette, 1980). 

Geochemical surveys of areas having political boundaries may be of particular local usefulness and interest, such 

as the multimedia geochemical survey of the U.S. Geological Survey coordinated with State agencies of Missouri 

(Erdman and others, 1976a,b; Tidball, 1976, 1984a,b; 

Connor and Ebens, 1980; Ebens and Connor, 1980; and 

Feder, 1982b) (fig. 3.5). A geochemical study of Kentucky 

focused on rock units (Connor, 1975; 1981a-c) and soils 

and plants (Tidball, 1975). A survey of elements in soils 

and plants of Alaska has been completed recently (Gough 

and others, 1984, 1988) (fig. 3.6). 

Many references to the abundance of various elements in soils and plants are available in current literature, 

including general reference books, textbooks, and journal 

articles (see, for example, Clarke and Washington, 1924; 

Turekian and Wedepohl, 1961; Vinogradov, 1959; Kovalevskii, 1979; Rose and others, 1979; Davies, 1980; 

Brooks, 1983; and Kabata-Pendias and Pendias, 1984). 

These sources are useful in explaining geochemical processes, providing case histories of geochemical projects, 

and even in giving regional, or worldwide, estimates of the 

abundance of many elements in a great variety of natural 

materials. In many of these references, however, important 

information necessary for judging the reliability of the data 

is omitted or inadequately explained due to lack of space. 

To evaluate the usefulness of the grand means, ranges, 

norms, or baselines of element concentrations, information 

The State of Soil and Plant Geochemical Surveys 11 
50° 

--------

440 

WYOMING 

43° --

• Regina 1 

I 

~ I MANITOBA 

, 

l 

I 

I 

----------r------- _L ____ _ 

SOUTH DAKOTA 

L_ ______________________ _ 

I NEBRASKA 

! r . ''f I 2yo _KILOMETE~ \ 

I 0 100 200 MILESl 42~ ~-~--~L----L--~L_--~ __ 1 _ll! ____ i_ __ _l ______ LI ____ LI __ 

Figure 3.1. Example of a regional geochemical study using various sampling materials. Open circles indicate localities 

where the A and C horizons of soil, western wheatgrass, silver sagebrush, and above-ground plant biomass were sampled 

in the northern Great Plains Province. From Ebens and Shacklette (1982). 

12 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
1/ff' 

36" 

34" 

32" 

30" 

24° 

22" 

1111" 

I 

lo.orn.nc~;2.1 Geomltricdlvlllion' 1.79 

1-of-lnd-.1.210 

v--l'tMIIII,...2~~fil~ 

IWOUNT ... PARTSP£11MILUON 

111i" 114° 112" 110" 1111" 

36" 

30" 

!illOMUS 24" 

22" 

111" 104° 102" 100" !Ill" 811" 116" 82" 74" 

Figure 3.2. Example of a regional geochemical study of soils and plants encompassing the entire conterminous United 

States-a geochemical study of the broadest scale showing vanadium content of surficial materials. From Shacklette and 

Boerngen (1984). 

on some or all of the following characteristics of the 

investigation may be essential: 

( 1) Description of the objectives and areal extent of the 

study on which the data were based; 

(2) Definition of the objectivity of the sampling plan that 

was used (for reduction of sampling bias, including the 

basis on which sampling sites were selected); 

(3) Adequate descriptions of the sampling media (plant 

species, soil types or origins, and so on); 

(4) Description of the analytical methods used in determining element concentrations in the samples and the 

sensitivity (limits of quantitative determination) of the 

methods; 

(5) Degree of randomization of the sequence of samples 

before submission to the analysts, to reduce the effects 

of error associated with instrumental imprecision and 

operator bias; 

(6) Information on the disposition made of reported element concentrations that were censored (having less 

than, or greater than, the limits of quantitative determination of the analytical method that was used) and the 

ratio of the number of samples in which the element 

was found in measurable concentrations to the number 

of samples analyzed; 

(7) Clear identification of the means and deviations as 

arithmetic and standard or, preferably, geometric for 

most elements in soils and plants; 

(8) Description of the basis used for the reported analytical 

values for a sample; that is, wet or dry weight, ash or 

dried material, extractable or total element concentrations, whole stream sediments or concentrates, and so 

on; and 

(9) Use of analysis of variance methods to determine at 

what level of the sampling plan (within sites, among 

sites, among regions) and from what source (sampling 

or analytical procedures) the greatest and least variances are found. If, for example, an excessive amount 

of the variance is due to sampling or analytical procedures, reliable estimates of means or baselines for these 

data cannot be confidently determined. 

The term "geochemical baseline" is often used to 

express an expected range of element concentrations around 

a mean in a "normal" sampling medium. The baseline 

would then depend on the limits of the range that are 

The State of Soil and Plant Geochemical Surveys 13 
0 100 200300 

I I I I 

KM 

I 

I 

' I 

I 

' 

Figure 3.3. Example of a regional geochemical study for one type of sampling material-location of 50-km2 sampling sites 

and the general distribution of big sagebrush (bold, dashed lines modified from Beetle, 1960) in eight physiographic 

provinces (province boundaries after Fenneman, 1931). From Gough and Erdman (1982). 

14 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
I 

I 

~..------J ' '\ 

20 

' \ 

\ ', ,~-, 

""'""._r '\ 

"' ~ 

0 

\ 

' ' \ 

' ' 

'--~ 

Symbol and percentage of total samples 

represented by symbol 

: C> I .. : M 

"' M "' I (} I Q I ,. I I 

: ~ 

~ 

I • ~ I I lr-_1 I >-

(.) 

z 

LU 

~ 10 LU 

a: 

LL 

~ 

~ - r--

f--

f--

f--

I I 

Q c 0 0 0 0 c 0 0 M ~ ~ 0 ~ 0 0 0 0 

0 0 0 ~ ~ N M ~ ~ 

SODIUM, IN PERCENTAGE IN ASH 

Geometric mean, 2.2 

Geometric deviation, 4.05 

Number of samples and analyses, 123 

-

-

I _j_ __ ]_ 

0 100 200 300 

. ·: ... ,.-· 

N 

1 

400 500 MILES 

0 100 200 300 400 500 KILOMETERS 

Figure 3.4. Example of a regional geochemical study in which airborne chemical elements in plants are sampled. Symbols 

indicate sodium content in Spanish moss. From Shacklette and Connor (1973). 

chosen. Tidball and Ebens (1976) proposed that, as a 

reasonable limit on this range, a baseline should encompass 

the central 95 percent of the observed concentrations 

because, due to chance alone, samples reflecting natural 

conditions are expected to fall outside this range only about 

5 percent of the time. They stated further that statistical 

properties of the observed data are more realistic if based on 

lognormal distribution theory (Miesch, 1976). The expected 

range may then be expressed as the average of the logarithms ±2 standard deviations of the logarithms. The upper 

and lower concentration limits of the baseline may be 

expressed on an arithmetic scale by finding the antilogarithms of the logarithmic limits. The same limits also may 

be computed for the geometric mean (GM), which is the 

The State of Soil and Plant Geochemical Surveys 15 
.,. 

0 

.,. 9 2' 

I 

I 

~ ' ' ), ,.. 

/ '"" 

50 100 MILES 

50 100 KILOMETRES 

Figure 3.5. Example of a geochemica l survey of areas 

having political boundaries. Vegetation-type areas are 

classified according to the average concentration of selenium in sumac from Missouri. Each number on the map is 

antilogarithm of the logarithmic mean, and the geometric 

deviation (GD), which is the antilogarithm of the logarithmic standard deviation. The 95.4-percent expected range 

lies between GM/(GD)2 and GM· (GD)2 . Therefore, to 

evaluate a proposed baseline for use in geochemical studies 

of the environment, adequate statistics must be given in a 

report. 

For more than a decade, scientists of the U.S. 

Geological Survey who specialize in the geochemistry of 

rocks, soils, and plants, as well as in other natural materials, have conducted environmental studies that complied 

with all or most of the procedures listed above to provide 

scientifically defensible geochemical data. These studies, 

GEOMETRIC MEAN, 

SELENIUM, IN PARTS 

PER MILLION 

11111 .023 

0 .013 

c=J .01 

25~Fiood-plain Forest 

GM 0.027 . . GD 1.98 

0 . 

Glaciated Prairie 

GM 0.022 

GD 1.83 

z 

w 

~ll :::> 

Unglaciated Prairie 

GM 0.013 

GD 1.62 

0 

w 

a: 

u. "[L 

0 

Cedar Glade 

GM O.D1 

GD 1.44 

Oak·hickory Forest 

GM 0.01 GD 1.43 

25L0ak·hickory-pine Forest 

GM O.D1 

GD 1.35 

0 ..- CD N Q) 

0 s s ~ ~ cicic:icici 

A 

SELENIUM. IN PARTS PER MILLION 

the geometric mean concentration of selenium in generally five samples from a 7.5-minute quadrangle. From 

Erdman and others (1976a). 

some of which are cited in this report, have been made of 

areas of many sizes and diverse landscape types where the 

concentrations of naturally occurring or artificially introduced chemical elements in soils and plants are evaluated. 

The toxicity levels of many elements to plants, animals, and 

man also have been reviewed (Gough and others, 1979). 

These data bases have been developed for soils and plants in 

environmental studies and probably are unparalleled in 

scope and reliability . Results of these studies have been 

presented in U.S. Geological Survey publications, as well 

as in other scientific journals and books. Many of the 

reported geochemical data, and some unpublished data, are 

held in computer files that can be readily accessed . 

16 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
-1 

:r 

I'D 

r.ll 

g 

I'D 

0 

r.ll -

~ 

~ 

j 

Q. 

~ 

Qj" 

a 

~ 

I'D 

0 

t") 

:r 

I'D 

3 

;:;-

e!. 

r.ll 

c 

~ I'D 

~ 

" 

6'c9o 

/ 

/ d / 

\)C:J~_.,-/ .,........-\)C;, 

~ 

180° 

/J. "-•o 0 

... ~8 

" 

0 300 600 KILOMETERS 

0 100 200 300 MILES 

176° 

Figure 3.6. Example of a geochemical survey of areas having political boundaries. Solid squares indicate location of sampling sites for soil and plant 

geochemistry, Alaska. This is a geochemical study of the broadest scale. From Gough and others (1988). 
REFERENCES CITED 

Beetle, A.A., 1960, A study of sagebrush, the section Tridentatae 

of Artemisia: University of Wyoming, Agricultural Experiment Station Bulletin 368, 83 p. 

Brooks, R.R., 1983, Biological methods of prospecting for 

minerals: New York, John Wiley and Sons, 322 p. 

Clarke, F.W., and Washington, H.S., 1924, The composition of 

the Earth's crust: U.S. Geological Survey Professional 

Paper 127, 117 p. 

Connor, J.J., 1975, Sandstone, shale, and carbonate rocks of 

Paleozoic age in Kentucky, study No. 5, in Connor, J .J., 

and Shacklette, H.T., Background geochemistry of some 

rocks, soils, plants, and vegetables in the conterminous 

United States: U.S. Geological Survey Professional Paper 

574-F, p. F6. 

---1981a, Geochemical analyses and summaries of carbonate 

rocks from Kentucky: U.S. Geological Survey Open-File 

Report 81-509, 121 p. 

---1981b, Geochemical analyses and summaries of Mississippian and Pennsylvanian sandstone from Kentucky: U.S. 

Geological Survey Open-File Report 81-1098, 91 p. 

---1981c, Geochemical analyses and summaries of shale from 

Kentucky: U.S. Geological Survey Open-File Report 

81-1097, 116 p. 

Connor, J.J., and Ebens, R.J., 1980, Geochemistry of bedrock 

units in Missouri and parts of adjacent States: U.S. Geological Survey Professional Paper 954-F, 55 p. 

Connor, J.J., and Shacklette, H.T., 1975, Background geochemistry of some rocks, soils, plants, and vegetables in the 

conterminous United States: U.S. Geological Survey Professional Paper 574-F, 168 p. 

---1984, Factor analysis of the chemistry of Spanish moss: 

U.S. Geological Survey Professional Paper 574-I, 120 p. 

Davies, B.E., ed., 1980, Applied soil trace elements: New York, 

John Wiley and Sons, 482 p. 

Ebens, R.J., and Connor, J.J., 1980, Geochemistry of loess and 

carbonate residuum: U.S. Geological Survey Professional 

Paper 954-G, 32 p. 

Ebens, R.J., and Shacklette, H.T., 1982, Geochemistry of some 

rocks, mine spoils, stream sediments, soils, plants, and 

waters in the western energy region of the conterminous 

United States: U.S. Geological Survey Professional Paper 

1237, 173 p. 

Erdman, J.A., and Gough, L.P., 1982, Miscellaneous small 

grains from the northern Great Plains, study No. 21, in 

Ebens, R.J., and Shacklette, H.T., Geochemistry of some 

rocks, mine spoils, stream sediments, soils, plants, and 

waters in the western energy region of the conterminous 

United States: U.S. Geological Survey Professional Paper 

1237, p. 19. 

Erdman, J.A., Shacklette, H.T., and Keith, J.R., 1976a, Elemental composition of selected native plants and associated 

soils from major vegetation-type areas in Missouri: U.S. 

Geological Survey Professional Paper 954-C, 87 p. 

---1976b, Elemental composition of corn grains, soybean 

seeds, pasture grasses, and associated soils from selected 

areas in Missouri: U.S. Geological Survey Professional 

Paper 954-D, 23 p. 

Feder, G .L., 1982a, Ground water chemistry, Poplar River Basin, 

Montana and Saskatchewan, study No. 27, in Ebens, R.J., 

and Shacklette, H.T., Geochemistry of some rocks, mine 

spoils, stream sediments, soils, plants, and waters in the 

western energy region of the conterminous United States: 

U.S. Geological Survey Professional Paper 1237, p. 24. 

---1982b, Geochemical survey of waters of Missouri: U.S. 

Geological Survey Professional Paper 954-E, 77 p. 

Fenneman, N .M., 1931, Physiography of Western United States: 

New York, McGraw Hill, 714 p. 

Gough, L.P., and Erdman, J.A., 1982, Big sagebrush from eight 

western physiographic provinces, study No. 23, in Ebens, 

R.J., and Shacklette, H.T., Geochemistry of some rocks, 

mine spoils, stream sediments, soils, plants, and waters in 

the western energy region of the conterminous United 

States: U.S. Geological Survey Professional Paper 1237, 

p. 21. 

Gough, L.P., Peard, J.L., Severson, R.C., Shacklette, H.T., 

Tompkins, M.L., Stewart, K.C., and Briggs, P.H., 1984, 

Chemical analyses of soils and other surficial materials, 

Alaska: U.S. Geological Survey Open-File Report 84-423, 

79 p. 

Gough, L.P., and Severson, R.C., 1981, Element concentrations 

in rehabilitation species from thirteen coal stripmines in 

five Western States and Alaska: U.S. Geological Survey 

Open-File Report 81-182, 118 p. 

Gough, L. P. , Severson, R. C. , and Shacklette, H. T. , 1988, 

Element concentrations in soils and other surficial materials 

of Alaska: U.S. Geological Survey Professional Paper 

1458, 53 p. 

Gough, L.P., Shacklette, H.T., and Case, A.A., 1979, Element 

concentrations toxic to plants, animals, and man: U.S. 

Geological Survey Bulletin 1466, 80 p. [Reprinted.] 

Kabata-Pendias, Alina, and Pendias, Henryk, 1984, Trace elements in soils and plants: Boca Raton, Fla., CRC Press, 

315 p. 

Kovalevskii, A.L., 1979, Biogeochemical exploration for mineral 

deposits: New Delhi, Amerind Publishing Co., 136 p. 

McNeal, J.M., 1982, Stream-sediment chemistry in the northern 

Great Plains, study No. 6, in Ebens, R.J., and Shacklette, 

H.T., Geochemistry of some rocks, mine spoils, stream 

sediments, soils, plants, and waters in the western energy 

region of the conterminous United States: U.S. Geological 

Survey Professional Paper 1237, p. 9. 

Miesch, A. T., 1976, Sampling designs for geochemical surveysSyllabus for a short course: U.S. Geological Survey OpenFile Report 76-772, 138 p. 

Miesch, A.T., and HuffmEn, Claude, Jr., 1972, Abundance and 

distribution of lead, zinc, cadmium, and arsenic in soils, 

chap. 4, in U.S. Environmental Protection Agency, Helena 

Valley, Montana area environmental pollution study: Environmental Protection Agency Office of Air Programs, 

Research Triangle Park, 179 p. 

Rose, A.W., Hawkes, H.E., and Webb, J.S., 1979, Geochemistry in mineral exploration (2d ed.): New York, Academic 

Press, 657 p. 

Schultz, L.G., Tourtelot, H.A., Gill, J.R., and Boerngen, J.G., 

1980, Composition and properties of the Pierre Shale and 

equivalent rocks, northern Great Plains region: U.S. Geological Survey Professional Paper 1064-B, 114 p. 

18 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Severson, R.C., and Tidball, R.R., 1982, Total soil chemistry, 

northern Great Plains, study No. 16, in Ebens, R.J., and 

Shacklette, H.T., Geochemistry of some rocks, mine 

spoils, stream sediments, soils, plants, and waters in the 

western energy region of the conterminous United States: 

U.S. Geological Survey Professional Paper 1237, p. 16. 

Shacklette, H.T., 1980, Elements in fruits and vegetables from 

areas of commercial production in the conterminous United 

States: U.S. Geological Survey Professional Paper 1178, 

149 p. 

Shacklette, H.T., and Boerngen, J.G., 1984, Element concentrations in soils and other surficial materials of the conterminous United States: U.S. Geological Survey Professional 

Paper 1270, 105 p. 

Shacklette, H.T., and Connor, J.J., 1973, Airborne chemical 

elements in Spanish moss: U.S. Geological Survey Professional Paper 574-E, 46 p. 

Tidball, R. R. , 197 5, Soils and plants in Kentucky, I and II, study 

Nos. 18 and 19, in Connor, J.J., and Shacklette, H.T., 

Background geochemistry of some rocks, soils, plants, and 

vegetables in the conterminous United States: U.S. Geological Survey Professional Paper 574-F, p. F9. 

---1976, Chemical variation of soils in Missouri associated 

with selected levels of the soil classification system: U.S. 

Geological Survey Professional Paper 954-B, 16 p. 

---1984a, Geography of soil geochemistry of Missouri agricultural soils: U.S. Geological Survey Professional Paper 

954-H, 54 p. 

---1984b, Geochemical classification by factor analysis of 

Missouri agricultural soils: U.S. Geological Survey Professional Paper 954-I, 19 p. 

Tidball, R.R., and Ebens, R.J., 1976, Regional geochemical 

baselines in soils of the Powder River Basin, MontanaWyoming, in Laudon, R.B., ed., Geology and energy 

resources of the Powder River, Wyoming Geological Association 28th annual field conference, guidebook: Casper, 

Wyo., Wyoming Geological Association, p. 229-310. 

Turekian, K.K., and Wedepohl, K.E., 1961, Distribution of the 

elements in some major units of the Earth's crust: Geological Society of America Bulletin, v. 72, no. 2, p. 175-192. 

Vinogradov, A.P., 1959, The geochemistry of rare and dispersed 

chemical elements in soils (2d ed.): New York, Consultants 

Bureau Enterprises, 209 p. 

The State of Soil and Plant Geochemical Surveys 19 

4. Geochemical Studies-The Missouri Experience 

By A.T. Miesch 

The field and laboratory methods used in geochemistry by the U.S. Geological Survey (USGS) were developed primarily for mineral-resource assessment programs. 

As early as 1952, however, a few USGS geochemists and 

other scientists became involved with problems of 

geochemistry that were related to human and animal health 

and with the use of geochemical methods for recognizing 

and defining environmental pollution. These limited efforts, 

and the USGS's established leadership in geochemistry, 

enabled medical scientists and health officials to recognize 

the potential importance of USGS work in environmental 

studies. Over the past 30 years, the results of a great many 

topical studies in geochemistry and health and environmental geochemistry, many done in collaboration with medical 

researchers, have been published in USGS reports and 

scientific journals. One of the most extensive efforts in 

support of medical research was carried out in Missouri. 

In 1968, the USGS was approached by the Environmental Health Surveillance Project of the University of 

Missouri to participate in a cooperative multidisciplinary 

study of geochemistry and health-disease relations throughout Missouri. The group was led by an epidemiologist and 

included a health statistician, as well as agriculturists and 

about a dozen other scientists associated with the university. 

The basic approach was to accumulate data and compile 

statewide maps showing variations in health and disease 

characteristics in both human and animal populations, 

particularly birth defects in swine. The rationale for studying swine was that more than 3 million piglets were born in 

Missouri each year, whereas human births numbered no 

more than 100,000 annually, thus swine provided a much 

larger sample for statistical purposes. The scientists also 

showed substantive evidence indicating that health statistics 

pertaining to swine had a bearing on the human population 

(Marienfeld, 1972). 

The Environmental Health Surveillance Project asked 

the USGS to design and conduct a program to describe the 

geochemical variability in the rock substrate, soils and other 

surficial geologic materials, natural and agricultural vegetation, and ground and surface waters throughout the State. 

The USGS accepted the challenge not only because of the 

possibility of lending support to the project, but also 

because of the opportunity to develop and explore methods 

for collecting geochemical data specifically for use in 

epidemiological surveys. Until that time, most of the data 

collected in health and environmental studies were from 

small regions and had been meant for very specific purposes. In Missouri, the geochemical landscape was to be 

described over a broad geologically diverse area in a way 

that would support not only the ongoing epidemiological 

studies but also any other environmental investigations that 

might be conducted in the future. For this purpose, a group 

composed of three geologists-geochemists, three botanists 

experienced in field geochemistry, a soil scientist, a 

hydrologist-geochemist, a statistical clerk, and several parttime personnel was assembled. The group also had the 

benefit of the USGS's extensive analytical laboratories and 

experienced analytical chemists, as well as support in 

computing, library research, technical illustration, and 

manuscript preparation. Analytical support included truckmounted field laboratories in a few situations where special 

onsite analytical work was needed. 

There was never a doubt that the USGS team could 

provide a great deal of geochemical information that could 

be useful to the Missouri project. As essentially no 

geochemical information of a regional nature was available, 

almost any sort of systematic sampling and analytical 

program conducted on a statewide scope could have yielded 

useful results. The problem was to make the best possible 

use of field and laboratory resources in providing the most 

pertinent geochemical data possible. Because the data were 

to be examined in relation to data on health and disease, it 

was also imperative to describe geochemical variations in a 

manner that was statistically defensible. Statistical defensibility has never been a matter of great concern in geochemistry for mineral exploration because the only geochemical 

variations likely to be of interest are so large that statistical 

evaluation is unnecessary. However, it was clear that the 

magnitudes of geochemical variability that might be related 

to health abnormalities were almost totally unknown and 

that small subtle geochemical variations could not be 

dismissed as unimportant. It was important only that identified variations be real rather than statistical aberrations or 

at least that the reported variations carry associated levels of 

confidence or probability. Clearly, the new methods to be 

used would require heavy use of formal experimental design 

Geochemical Studies-The Missouri Experience 21 
procedures. To assure that the estimated probabilities were 

unbiased, it would be necessary to use strict randomization 

procedures in both the field and laboratory. 

The project members, subject matter specialists 

(geologists, soil scientists, botanists, and hydrologists), 

were each aware of where to expect the major geochemical 

variations within the rocks, soils, vegetation, and waters of 

the State. These variations occur among the major subdivisions recognized within each medium. The major subdivisions in the bedrock, for example, are based on rock type 

and geologic age; those for soils follow the taxonomic 

groups of the soil classification system; those for water are 

based on hydrologic units, and those for vegetation vary 

according to taxonomy and predefined vegetation-type 

areas. The first task, one that would yield the most 

geochemical information the most rapidly and for the lowest 

cost, was obviously to describe the nature and magnitude of 

the geochemical differences among these major categories. 

This task, carried out for each sample medium, was Phase 

I of a proposed general approach (Connor and others, 1972; 

Miesch, 1976) to any reconnaissance geochemical survey of 

this kind. The purpose of Phase I sampling is to define the 

major geochemical variations associated with the broad 

regional subdivisions in the material being studied. Phase I 

sampling may include two stages. Stage 1 consists of 

preliminary sampling to make estimates of the variations 

present so that the final sampling in stage 2 can be planned. 

The estimates of variation are used to select the optimum 

number of samples in stage 2 for describing as many 

geochemical differences as possible for any selected level of 

significance. The general approach is known to statisticians 

as a two-stage sampling strategy (Stein, 1945). Phase II 

sampling, in the general approach, consists of sampling to 

describe geochemical variations within major classifications 

of the media. It also consists of two stages, one to estimate 

an efficient sample-spacing interval and another to carry out 

the final sampling. None of the Missouri work progressed 

beyond Phase I. 

The major results of the geochemical survey of 

Missouri are published in a series of seven 6-month 

progress reports issued to the University of Missouri's 

Environmental Health Surveillance Project (USGS, 

1972a-f, 1973) and in USGS Professional Paper 954, which 

contains chapters on methodology (Miesch, 1976); soils 

(Tidball, 1976, 1984a,b); natural vegetation, agricultural 

plants, and associated soils (Erdman and others, 1976a,b); 

ground and surface water (Feder, 1979); bedrock (Connor 

and Ebens, 1980); and surficial geologic deposits (Ebens 

and Connor, 1980). 

Support for the USGS's part in the Missouri program 

waned after it became clear that regional abnormalities in 

health and disease being sought by the Environmental 

Health Surveillance Project were more difficult to identify 

than the geochemical variations. The regional patterns in 

the health data simply showed no clear relation to the 

geochemical patterns the USGS had identified. Perhaps no 

such relations exist, perhaps they are present but extremely 

subtle, or perhaps the wrong epidemiological or the wrong 

geochemical data were collected. Nevertheless, the collaborative program between the USGS and the Environmental 

Health Surveillance Project was a sincere effort and a 

logical strategy for attacking a problem that is still important. However, no effort such as this can continue very long 

without the excitement of useful results to encourage its 

participants and continue the necessary funding. 

On the positive side, the State of Missouri has been 

covered by, at least, the first phase of a statistically sound 

geochemical survey, and it is the only State so fortunate. 

The data have already proved useful in helping to resolve 

several problems in possible metal pollution, some of which 

are related to waste-disposal practices (Connor and others, 

1970; Ebens and others, 1973; Wallace B. Howe, written 

commun., 1986). It is reasonable to expect many additional 

uses in the future, as the geochemical maps and other data 

produced in the Missouri experience will always be there 

for continuing epidemiological studies. 

REFERENCES CITED 

Connor, J.J., and Ebens, R.J., 1980, Geochemistry of bedrock 

units in Missouri and parts of adjacent States: U.S. Geological Survey Professional Paper 954-F, 55 p. 

Connor, J.J., Erdman, J.A., Sims, J.D., and Ebens, R.J., 1970, 

Roadside effects on trace element content of some rocks, 

soils, and plants of Missouri, in Hemphill, D.D., ed., 

Trace substances in environmental health, IV, Proceedings 

of University of Missouri 4th annual conference on trace 

substances in environmental health, June 23-25, 1970: 

Columbia, Mo., University of Missouri, p. 26-34. 

Connor, J.J., Feder, G.L., Erdman, J.A., and Tidball, R.R., 

1972, Environmental geochemistry in Missouri-A multidisciplinary study, in Earth sciences and the quality of life, 

Symposium 1: Montreal, Canada, 24th International Geologic Congress, p. 7-14. 

Ebens, R.J., and Connor, J.J., 1980, Geochemistry of loess and 

carbonate residuum: U.S. Geological Survey Professional 

Paper 954-G, 32 p. 

Ebens, R.J., Erdman, J.A., Feder, G.L., Case, A.A., and Selby, 

L.A., 1973, Geochemical anomalies of a claypit area, 

Callaway County, Mo., and related metabolic imbalance in 

beef cattle: U.S. Geological Survey Professional Paper 

807, 24 p. 

Erdman, J.A., Shacklette, H.T., and Keith, J.R., 1976a, Elemental composition of selected native plants and associated 

soils from major vegetation-type areas in Missouri: U.S. 

Geological Survey Professional Paper 954-C, 87 p. 

---1976b, Elemental composition of corn grains, soybean 

seeds, pasture grasses, and associated soils from selected 

areas in Missouri: U.S. Geological Survey Professional 

Paper 954-D, 23 p. 

Feder, G.L., 1979, Geochemical survey of waters of Missouri: 

U.S. Geological Survey Professional Paper 954-E, 78 p. 

22 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Marienfeld, C.J., 1972, A field study relating geochemical environment to health and disease, in Hopps, H.C., and 

Cannon, H.L., eds., Geochemical environment in relation 

to health and disease: Annals of the New York Academy of 

Sciences, v. 199, p. 335-348. 

Miesch, A. T., 1976, Geochemical survey of Missouri-Methods 

of sampling, laboratory analysis, and statistical reduction of 

data: U.S. Geological Survey Professional Paper 954-A, 

39 p. 

Stein, C., 1945, A two-sample test for a linear hypothesis whose 

power is independent of the variance: Annals of Mathematical Statistics, v. 16, p. 243. 

Tidball, R.R., 1976, Chemical variation of soils in Missouri 

associated with selected levels of the soil classification 

system: U.S. Geological Survey Professional Paper 954-B, 

16 p. 

---1984a, Geography of soil geochemistry of Missouri agricultural soils: U.S. Geological Survey Professional Paper 

954-H, 54 p. 

---1984b, Geochemical classification by factor analysis of 

Missouri agricultural soils: U.S. Geological Survey Professional Paper 954-1, 19 p. 

U.S. Geological Survey, 1972a, Geochemical survey of 

Missouri-Plans and progress for the first six-month period 

(July-December, 1969): U.S. Geological Survey Open-File 

Report 72-398, 49 p. 

---1972b, Geochemical survey of Missouri-Plans and 

progress for the second six-month period (January-June, 

1970): U.S. Geological Survey Open-File Report 72-399, 

60 p. 

---1972c, Geochemical survey of Missouri-Plans and 

progress for the third six-month period (July-December, 

1970): U.S. Geological Survey Open-File Report 72-400, 

33 p. 

---1972d, Geochemical survey of Missouri-Plans and 

progress for the fourth six-month period (January-June, 

1971): U.S. Geological Survey Open-File Report 72-401, 

63 p. 

---1972e, Geochemical survey of Missouri-Plans and 

progress for the fifth six-month period (July-December, 

1971): U.S. Geological Survey Open-File Report 72-402, 

145 p. 

---1972f, Geochemical survey of Missouri-Plans and 

progress for the sixth six-month period (January-June, 

1972): U.S. Geological Survey Open-File Report 72-403, 

86 p. 

---1973, Geochemical survey of Missouri-Plans and 

progress for the seventh six-month period (June-December, 

1972): U.S. Geological Survey Open-File Report 73-326, 

59 p. 

Geochemical Studies-The Missouri Experience 23 

5. Written Communication on Environmental 

Geochemistry in Missouri 

By Wallace B. Howe to Bruce R. Doe 

January 31, 1986 

Dr. Bruce Doe 

Assistant Chief Geologist 

Eastern Region 

Geologic Division 

U.S. Geological Survey 

Reston, VA 22092 

Dear Bruce: 

I am writing in connection with your phone call and 

our discussion of January 15th, regarding efforts of the 

USGS to develop directions in environmental geochemistry. I am also providing a little more information on an 

attempt we made some years ago to develop interest in a 

study of natural background radiation levels in the State. 

Concerning environmental chemistry first, I have 

discussed your question with people here, and it is quite 

clear that there has been more use of the Shacklette and 

Tidball geochemical survey of the State than I had been 

aware of or was able to recall in our discussion. Applications of that survey that we are able to identify at this time 

include the following: 

1. Its use in connection with attempts to resolve a case of 

livestock poisoning by molybdenum in drainage from a 

strip mine site in Callaway County, Missouri. I believe 

that this effort actually more or less coincided with some 

part of the field sampling. 

2. A broad characterization of the trace-element distribution in alluvial sediments along the Missouri River and 

its tributaries in the Kansas City, Missouri, area, where 

there was a need for background-level information on a 

number of trace-element occurrences. 

3. Its use in providing information on background levels of 

a number of elements present at the surface in soils and 

rock in the vicinity of a large hazardous-waste disposal 

site in Warren County, Missouri. 

4. An additional use was the establishment of background 

levels at several sites where there has been land spreading or irrigation for waste disposal purposes. A specific 

example is a site where costly, time-consuming litigation was avoided because background information of 

certain metals was available. 

5. There was a section on heavy-metal (Cu, Pb, Zn, and 

Ba) anomalies in the loess and carbonate residuum in the 

Washington County area, southeast Missouri, in USGS 

P954-G (1980), that had implications in the Rolla 

2-Degree Project. 

6. Its use as reference in Extraordinary Trace-Element 

Accumulations in Roadside Cedars near Centerville, 

Missouri: USGS P750-B, 1971, p. 1351-1356 (probably from Pb concentrate spills from trucks). 

As you know, much effort has been expended on 

specific geochemical problems concerning contamination. 

The issues relate to identification of contaminants and 

potential remedial action. We have been extensively 

involved in assisting in sampling of innumerable sites in 

Missouri. However, most, if not all, of the laboratory and 

related work has been carried out by EPA or through other 

agencies. 

A good case could be made for expanding on the 

rather broad treatment of Shacklette and Tidball, perhaps 

focusing on areas that may deserve priority for one reason 

or another. The long-range objective would be development 

of more detailed trace-element and other key geochemical 

background data, in order to 1) demonstrate such an 

approach at state or regional level and 2) provide greater 

detail and more in-depth interpretation of the data. If the 

USGS would be interested in pursuing this general idea, 

either as a project to be carried out entirely by the USGS or, 

more desirably from our standpoint, one that we both might 

approach on a "joint funding" basis, we in the Missouri 

Department of Natural Resources would certainly like to be 

informed and would be happy to help in developing a 

proposal to suit either purpose. 

Sincerely yours, 

Wallace B. Howe 

Assistant Division Director 

Division of Geology and Land Survey 

Written Communication on Environmental Geochemistry in Missouri 25 

6. Soil Studies in the Northern Great Plains 

By Ronald R. Tidball 

INTRODUCTION 

A large area of the northern Great Plains covering 

parts of four States and Saskatchewan (fig. 6.1) is underlain 

by large resources of strip-mineable coal. Because of 

extensive surface disturbance caused by strip mines, contemporary legislation usually requires reclamation of the 

land surface to a condition that equals or is an improvement 

on the original condition. This report describes a type of 

study that has been done in several parts of the northern 

Great Plains. In each case, the geochemical condition of the 

soils (that is, total chemical composition) was determined 

prior to disturbance so that the degree of conformance to 

future reclamation requirements could be evaluated. 

The size of the area studied can cause the magnitude 

of the sampling task to be overwhelming, particularly if the 

sampling frequency is high. The sampling task requires an 

efficient experimental design based on a limited number of 

samples that provides estimates of the sources and magnitudes of variation, as well as possible estimates of average 

elemental concentrations in the sampled population. 

If a population is homogeneous (has a small amount 

of natural variation), then only one or a few samples are 

required to describe that population. If a population is 

heterogeneous (has a large amount of natural variation), 

then many samples are required to describe it. In either 

case, however, sampling error and analytical error must be 

considered as part of the total variation. We expect the 

diversity of soils from such a large area as the northern 

Great Plains coal region to be large. Sources of variation 

include, but are not limited to, lithology, stratigraphy, 

climatic zones, vegetation types, soil properties, and degree 

of soil development. Any prior knowledge that would 

facilitate subdividing these diverse soils into more homogeneous chemical groups would help to reduce some of the 

variation and reduce the sampling requirements for estimating stable means. However, if prior knowledge is scarce, 

estimating as many sources of variation as affordable should 

be provided for. In addition to defining variation, we also 

hope to estimate geochemical baselines. 

A baseline may be viewed as a collection of data 

points, each defined as the natural value of a given 

geochemical measurement in a given sample. Baselines 

generally are established from data collected from materials 

confined within an area of interest. However, sometimes 

extrapolating a geochemical measurement from one area to 

another is desirable, and this raises the question of how far 

such a measurement can be extrapolated. 

Studies in the Powder River Basin, Wyo. (Tidball 

and Ebens, 1976; Connor, Keith, and Anderson, 1976), 

suggest that individual geochemical measurements of soil 

cannot be extrapolated very far, but that a summary 

property of a group of samples may be extrapolated over 

much larger distances depending on the magnitude of the 

larger scaled features of the variation. The following 

common geochemical situation in soil studies illustrates 

how variation affects the ability to extrapolate data. 

I 

I 

I 

Northern Great Plains 

j coal region 

I I NEBRAsKA ______ _ 

I 

0 100 200 300 KILOMETERS L..l ~-1...1 __ 1...1 _---.JI 

Figure 6.1. Location of the northern Great Plains coal 

region; area containing coal deposits of Tertiary age 

indicated by stipple pattern. From Severson and Tidball 

(1979). 

Soil Studies in the Northern Great Plains 27 
t 

z 

0 

~ 0: 

1-

z 

w 

u 

z 

0 

u 

A DISTANCE---+ 

t 

z 

0 

~ I Baseline g: 

z 

w 

u 

z 

0 

u 

8 

I Baseline 

DISTANCE___, 

Figure 6.2. Illustrations of hypothetical element distributions along traverses where the regional variation is either absent 

(A) or present (8). Baseline is shown as the 95-percent expected range. From Tidball and Ebens (1976). 

Assume that the concentration of some element in soil 

has been measured along two traverses; each element 

similarly exhibits large changes in concentration from one 

point to a nearby point (large local variation), but a regional 

(over larger distances ) component of variation is absent at 

one point (fig. 6.2A) and present in the other (fig. 6.2B). 

The large local variation indicates that extrapolation of 

individual measurements is risky except over very short 

distances. This inability to extrapolate individual measurements over more than short distances demonstrates the need 

for some measurement that can be extrapolated. A reasonable range of concentrations (a baseline) defined by the 

mean and standard deviation is such a measurement. The 

presence or absence of a regional component of variation, 

however, is crucial for determining how far the extrapolation may be extended. In the absence of a regional component (fig. 6.2A), the distance is large. In the presence of a 

regional component (fig. 6.2B), the distance is limited 

because of a regional trend; a series of more local baselines 

would better represent the situation. 

DEFINING THE POPULATION 

A population of objects or materials that is of interest 

to us is what we define it to be. The population of soils of 

the northern Great Plains is defined as the surface horizon of 

all the natural soils within the bounds of the coal-bearing 

region that are available for sampling. This is the target 

population. The set of samples that we collect is the sample 

population. Inferences about the target population are 

derived from the sample population. The target population 

is subject to various sources of variation; once we decide 

which of these sources can be measured, an appropriate 

experimental design can be selected. 

EXPERIMENTAL DESIGN 

Possible experimental designs include, but are not 

limited to, simple random sampling, stratified random 

sampling, systematic grid sampling, and nested analysis of 

variance (ANOV). Nested ANOV has been the design of 

choice because it facilitates partitioning the total variance 

into components, each of which is associated with a source 

of variation. 

The advantages of the nested ANOV are threefold. 

From a modest sample population, the variance components 

provide insight about (1) which sources of variation are 

important and which are not, (2) whether or not the initial 

sample population is sufficient to estimate stable means and 

baselines, and (3) whether the size of the sample population 

is statistically sufficient. If the sample population is shown 

to be adequate, then the data in hand provide an estimate of 

stable means and baselines. If the sample population is· 

insufficient, then we know to which source of variation to 

direct a resampling. 

THE NORTHERN GREAT PLAINS STUDY 

The sources of variation measured in the northern 

Great Plains were glaciated terrain versus nonglaciated 

terrain, four levels of decreasing distance from 100 km to 1 

km, and laboratory error (Severson and Tidball, 1979). An 

estimate of the magnitude of laboratory error with a 

threshold arbitrarily set at 50 percent of total variance helps 

to avoid interpreting error as a geographic effect. By 

partitioning the geographic part of the variance we determined the optimum method of data display (fig. 6.3) 

ranging in descending order of resolution from a stable map 

for elements having large regional variance to only a single 

value (grand mean) for the entire study area for elements 

having large local variance. The variance mean ratio 

28 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Yes 

No 

Yes 

Excessive analytical error, 

no 1nterpretat1on possible 

No 

100-km cell variance 

component 

100-km cell variance 

component significant not significant 

0 

® 

@ 

® 

c A 

Reproducible map based on 100-km cell means with contours, 

see fig. 6.4A, uranium. 

100-km cell mean is single best estimate for each cell, no map, 

see fig. 6.48, molybdenum . 

Terrain mean is single best estimate for each terrain, no map, 

see table 6.1, mercury. 

Grand mean is single best estimate for study area, no map, 

see table 6.2, boron. 

Figure 6.3. Flowchart for choice of optimum method of data display (either map or computed mean) depending on 

the presence of significant variance components. Significance is at 0.05 probability level; vm, variance mean ratio. 

Soil Studies in the Northern Great Plains 29 
A 

GM 2.3 

Range 1.7·3.1 

EWAN \MANITOBA 

I 

I ,21 ~'"~'"""""""":.:.:.::..:.:.::..:.:.: .;;.c;;.;;.;;.;·· ""·· · ----

Pierre 

0 

so• 

48° 

46° 

108° 

CANADA 

UNITEDSTATES 

106° 104° 102° 

SASKATCHEWAN \MANITOBA 

0 Regina 

I 

1.8 '3 2 ~.6 ,3~4 . . . ...,-{; l 

-------.----- ---- ,2.! ,3.3 ,4.4'\. 

,3.4 ~·~\ ·~~~8 ::·.: •

1

'\ 

Bismarck 

0, I 4.1 

,3.6 ,2.3 ,5.0 , 

N DAKOTA 

Billing~ 

MONTANA 

, ----csoAKOTA 

,3.3 ,4.4~3.5 ,2.e •e.li' 

---~ I 

44° 

,3.4 ,2\ i 

,2.7 ,1.3 I 

I 

Pierre 

0 

• ~Fi.\sK'A ____ _ 

1.9, GM 3.6 

Range 1.1·13 I 42'--~---L---L--~--~--~--~----~--~--.... ~ 

B 

0 100 200 300 400 KILOMETERS 

Figure 6.4. A, Uranium, 100-km cell means in parts per 

million (ppm), a mappable element having approximate 

contours. Patterned areas show frequency distribution in 

percent. Unpatterned area, less then 2.5 percent; light 

(Severson and Tidball, 1979, p. A7), vm, is the ratio of 

variance between different 100-km cells to that within 

individual cells. If the ratio is greater than one, a map of the 

cell means is considered to be stable and reproducible. 

An example of a mappable element is shown in figure 

6.4A for uranium. An example of a terrain mean is shown 

in table 6.1 for mercury. An example of an element that is 

best described by the means of individual 100-km cells is 

molybdenum (fig. 6.4B). The means are shown on a map to 

facilitate location, but no contour lines are shown. Both the 

mercury and molybdenum examples correspond to the case 

shown in figure 6.2B. An example of an element that is best 

described by a single grand mean is boron (table 6.2). This 

element corresponds to the case shown in figure 6.2A. 

OTHER DISTANCE-RELATED DESIGNS 

Several soil studies have been designed by using 

distances having varying intervals. The intervals may be 

expressed by either irregular-shaped areas and cells of 

varying size or actual distance between sampling localities 

stipple, 2.5-5.0 percent; medium-gray, 50-97.5 percent; 

dark gray, greater than 97.5 percent. 8, Molybdenum, 

100-km cell means (ppm), no contours. From Severson 

and Tidball (1979). 

Table 6.1. Terrain mean and baseline for mercury (in parts 

per million) in soil samples of each terrain when the 

difference between terrains is significant but the difference within terrains is not significant 

[Baseline, 95-percent expected range] 

Terrain Geometric mean Baseline 

Glaciated........................ 26 13-51 

Nonglaciated. . . . . . . . . . . . . . . . . . . . . 21 9-44 

Table 6.2. Grand mean and baseline for boron (in parts 

per million) in soil samples of entire study area when the 

difference between terrains is not significant 

[Baseline, 95-percent expected range] 

Element Geometric mean Baseline 

Boron .. . ... . ...•......•......... 41 18-96 

(barbell design; fig. 6.5). Some examples of studies that 

were designed by using areas of differing size similar to the 

northern Great Plains study include Connor, Keith, and 

Anderson (1976) in the Powder River Basin, Wyo.; Ringrose and others (1976) in the Piceance Creek Basin, Colo.; 

30 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
25 km 

X 

t------r--X 

X 

X 

X 

Figure 6.5. Diagrammatic representation of a barbell 

design. Sample localities shown as X's. From Severson 

(1979). 

Tidball and Severson ( 1977) in the oil shale region of 

Colorado and Utah; Tidball (1978) in the Powder River 

Basin, Mont.; and Severson (1978a) in northwest New 

Mexico. 

Examples of studies using the barbell design include 

Tidball and Ebens (1976) in the Powder River Basin, 

Mont.-Wyo.; Severson (1978b) in northwest New Mexico; 

and Severson (1979) in the Big Hom and Wind River 

Basins, Wyo.-Mont. 

THE GENERAL SAMPLING PLAN 

A general plan for geochemical sampling surveys of 

large regions was described by Connor and others (1972). 

The initial purpose is usually to distinguish the geochemical 

characteristics of some natural material that typically has 

mappable units. This general plan may be divided into at 

least four parts or stages, as follows: 

Phase 1: Sampling to describe differences among categories. 

Stage la: Preliminary sampling designed to determine 

the extent to which the categories are indeed geochemically distinct and to provide the basis for planning 

stage lb. 

Stage lb: Final sampling to derive reliable estimates of 

differences among categories and the amounts of 

compositional variability within each category. 

Phase 2: Sampling to describe patterns of variation within 

categories. 

Stage 2a: Preliminary sampling within each category to 

determine the sampling locality spacing that would be 

most efficient for describing the geochemical variation 

patterns within each category and the number of 

samples required from each locality. 

Stage 2b: Final sampling to describe the geochemical 

patterns within each category. 

The first phase, which commonly is based on a 

limited number of samples, results in a geochemical map 

that has relatively poor resolution, but one that may be 

adequate if the variability is mostly on a regional scale. The 

second phase usually requires a larger number of samples 

and results in a map that has a higher resolution. This phase 

is used if the variability is mostly on a local scale. 

The study in the northern Great Plains described 

above as well as other studies cited are all examples of stage 

la. Stage lb was never completed. Although a sequential 

progression through the stages leads to maximum efficiency, circumstances sometimes do not allow time to 

perform stage la or 2a (for example, see Tidball and others, 

this volume). 

When a stage lb- or 2b-type map is required as soon 

as possible, how can this mapping be accomplished? One 

technique is to apply a simple random or perhaps a stratified 

random design to cover the area of interest. Another 

technique is to sample on a systematic grid. In each case, 

either the number of random samples or the grid interval is 

selected on the basis of some prior knowledge about the 

expected variation, if available, or selected on the basis of 

resources available. Once collected, there is no assurance 

that the number of samples will be adequate. However, by 

simultaneously collecting a few additional samples according to an ANOV design and the random or grid samples, we 

can determine that ( 1) the data are faulty and therefore 

interpretations are risky or incorrect, (2) the number of 

samples is about optimum and interpretations are safe, or 

(3) interpretations are safe, but the number of samples is 

excessive. 

REFERENCES CITED 

Connor, J.J., Feder, G.L., Erdman, J.A., and Tidball, R.R., 

1972, Environmental geochemistry in Missouri-A multidisciplinary study, in Earth sciences and the quality of 

life- Symposium 1: Montreal, Canada, 24th International 

Geological Congress, Proceedings, p. 7-14. 

Connor, J.J., Keith, J.R., and Anderson, B.M., 1976, Tracemetal variation in soils and sagebrush in the Powder River 

Basin, Wyoming and Montana: U.S. Geological Survey 

Journal of Research, v. 4, no. 1, p. 49-59. 

Ringrose, C.D., Klusman, R.W., and Dean, W.O., 1976, Soil 

chemistry in the Piceance Creek Basin, in U.S. Geological 

Survey, Geochemical survey of the western energy regions, 

3d Annual Progress Report, July 1976: U.S. Geological 

Survey Open-File Report 76-729, p. 101-111. 

Severson, R.C., 1978a, Spatial variation in total element content 

in soils in northwest New Mexico and differences in soil 

composition at the Great Group taxonomic level, in U S. 

Geological Survey, Geochemical survey of the western 

energy regions, 5th Annual Progress Report, July 1978: 

U.S. Geological Survey Open-File Report 78-1105, 

p. 2-34. 

---1978b, Variation in element content of the Doak, 

Shiprock, and Sheppard soil association in New Mexico, in 

Soil Studies in the Northern Great Plains 31 
U.S. Geological Survey, Geochemical survey of the western energy regions, 5th Annual Progress Report, July 1978: 

U.S. Geological Survey Open-File Report 78-1105, 

p. 35-46. 

---1979, Regional soil chemistry in the Bighorn and Wind 

River basins, Wyoming and Montana: U.S. Geological 

Survey Professional Paper 1134-B, 9 p. 

Severson, R.C., and Tidball, R.R., 1979, Spatial variation in total 

element concentration in soil within the northern Great 

Plains coal region: U.S. Geological Survey Professional 

Paper 1134-A, 18 p. 

Tidball, R.R., 1978, Chemical and mineralogical evaluation of 

soils, Hanging Woman Creek EMRIA site, Big Horn 

County, Montana: U.S. Geological Survey Open-File 

Report 78-346, 88 p. 

Tidball, R.R., and Ebens, R.J., 1976, Regional geochemical 

baselines in soils of the Powder River Basin, MontanaWyoming, in Laudon, R.B., ed., Geology and energy 

resources of the Powder River, Wyoming Geological Association Guidebook, 28th annual field conference: Casper, 

Wyo., Wyoming Geological Association, p. 299-310. 

Tidball, R.R., and Severson, R.C., 1977, Chemical variation in 

alluvial soils of the oil shale region, in U.S. Geological 

Survey, Geochemical survey of the western energy regions, 

4th Annual Progress Report, July 1977: U.S. Geological 

Survey Open-File Report 77-872, p. 55-64. 

32 Proceedings of a U.S. Geological Survey Workshop on Environ...,ental Geochemistry 
7. Weathering Process Research-Pedology and Soil 

Geochemistry in Drainage Basins 

By Milan j. Pavich 

INTRODUCTION 

As part of the proposed National Environmental 

Geochemistry Program, there is a need for studies of 

rock-weathering and soil-forming processes. Several U.S. 

Geological Survey (USGS) geologists and pedologists (scientists studying the genesis and classification of soils) have 

conducted research involving environmental geochemistry. 

Papers such as those published by Markewich and others 

(1986, 1987, 1988) and Pavich (1986) are the result of 

cooperative research with the U.S. Department of Agriculture's Soil Conservation Service (SCS) and university 

laboratories. Research into the geochemical processes operating during pedogenesis is still in an incipient stage. The 

National Environmental Geochemistry Program provides an 

opportunity for more research into pedogenic processes. 

Unlike geochemical surveys, process studies are best done 

as interdisciplinary studies in drainage basins. 

The National Environmental Geochemistry Program 

can be divided into regional and topical studies; in many 

cases, these overlap. Soil geochemistry surveys are generally regional in scope, but specific topics or elements may 

be studied in areas as small as a single pedon, the unit of 

sampling comprising the A and B horizons and parent 

material, or in several pedons within a drainage basin. 

We have developed the sampling and analytical 

techniques needed to obtain high-quality data from regolith. 

For this report, regolith is defined as that material through 

which ground water flows before discharge at the Earth's 

surface or material from which domestic water supplies are 

obtained through springs or by pumping. Regolith generally 

comprises soil, weathered rocks, sediments, and fractured 

crystalline rocks. Crystalline rocks of low permeability are 

excluded. The following sections provide an outline of how 

soils can be studied as part of the National Environmental 

Geochemistry Program. 

DEFINITION OF SOIL 

Soil can be defined in many ways. For the purpose of 

geochemical analysis, the definition given by Birkeland 

(1984, p. 3) is useful: " ... a natural body consisting oflayers 

or horizons of mineral and/or organic constituents of variable thicknesses, which differ from the parent material in 

their morphological, physical, chemical, and mineralogical 

properties .... " This definition does not distinguish surface 

soils from buried soils. Study of the geochemical response 

of a specific soil to introduction of a specific element, or 

group of elements, usually involves the surface soil. In 

some cases, however, buried soils that have not been 

diagenetically altered since burial may provide useful geochemical information for comparison of past and present 

pedogenic environments (for example, climate, vegetation). 

Surface soils are mapped and classified in the United States 

according to taxonomic principles developed by the SCS 

(Soil Survey Staff, 1975). 

SOIL TAXONOMY 

The SCS Soil Taxonomy (Soil Survey Staff, 1975) 

classifies soils of the United States into 10 orders. These 

taxonomic divisions reflect a strong influence of climate, as 

seen on fig. 7.1, and also of parent material and physiographic setting. At present, we do not have sufficient 

knowledge to discuss the detailed evolution or genesis of 

individual suborders or soil series within these broader 

orders. 

The dominant soil orders in populated areas are 

mollisols, alfisols, and ultisols. Mollisols are distinguished 

by dark, organic-rich A horizons (mollie epipedon) and 

base saturation (a measure of exchangeable nutrients) 

greater than 50 percent throughout. Alfisols have lighter 

Weathering Process Research- Pedology and Soil Geochemistry in Drainage Basins 33 
w 

... 

"'Q 

0 

r"l 

,. 

,. 

c.. 

:r 

~ 

~ 

"' c: 

~ 

Cl 

~ 

0 

"" ;:;· 

!!!.. 

(J") 

!; 

"' ,. 

-< 

::;: 

~ 

~ :r 

0 

-c 

0 

:I 

rn 

:I 

a"' · 

:I 

3 

,. 

:I 

[ 

Cl 

~ r"l 

:r 

,. 

3 

~· 

-< 

Figure 7.1. Generalized soil map of the conterminous United States. Major soil groups represented by initial capital letters on map are as follows : A, alfisols; 

D, aridisols ; E, entisols; H, histosols; I, inceptisols; M, mollisols; S, spodosols; U, ultisols; V, vertisols. Modified from Soil Survey Staff (1975), where further 

information regarding soil taxa may be found. 
colored A horizons (ochric epipedon), an argillic (clayrich)horizon, and base saturation exceeding 35 percent in 

the argillic horizon. Ultisols are characterized by having 

base saturation less than 35 percent in the argillic horizon. 

In all of these soil orders, A and B horizons can be 

distinguished. 

HYDROCHEMICAL PROCESSES IN 

MAJOR SOIL ORDERS 

The full range of geochemical processes operating in 

these major soil orders is extremely complex. Identified 

capacities of soils that influence movement of chemical 

elements include: 

( 1) Cation-exchange capacity (CEC) of fine particulates 

(for example, clays, iron oxyhydroxides) and organic 

materials that are found in many soils. CEC is usually 

measured in terms of milliequivalents of cation per 100 

grams of solid (meq/100 g). Exchange capacities range 

from 2-4 meq/100 g for sesquioxides to 200 meq/100 g 

for humus (Tan, 1982). Base saturation is the percentage of CEC occupied by exchangeable bases (for 

example, Ca +2 , Mg +2 , K+, Na +). 

(2) The water-holding and infiltration capacities of soils 

runoff in response to rainfall. Runoff is an important 

characteristic of drainage basins that partially determines how dissolved and suspended materials, including pollutants, are moved from upland soils into 

surface-water discharge. 

Interaction between solids (for example, clay minerals, precipitated humic organic matter, other minerals) and 

elements entering the soil generally involves solid-solution 

chemical reactions, mainly at particulate surfaces. Surface 

reactions are varied and complex and are a topic of active 

research. Soil process studies should include surface chemistry. 

SAMPLING AND ANALYTICAL TECHNIQUES 

The geochemical assessment of any selected area 

requires a well-designed sampling scheme. For soil-survey 

work, the Soil Survey Staff (1984) has developed a scheme 

using transects, paired pedons, and satellite pedons. They 

stress that site selection should be based on choosing a 

pedon representative of the mapping unit and of the landscape being studied. Site selection is not random in their 

scheme. The same sampling schemes may not be appropriate to soil-genesis studies and geochemical surveys. 

Nested analysis of variance (Miesch, 1976) was used 

in the geochemical surveys of McNeal and others (1985) 

and Severson and Tidball (1979). They sampled mollisols 

in the northern Great Plains, an area of potential strip 

mining for coal. These studies demonstrate that efficient 

sampling schemes are possible for characterization of soil 

chemistry over a large area. Studies of soil genesis may 

require sampling schemes related more to the variability of 

parent material and landscape. 

CONTROL SECTIONS 

The drainage basin is the natural study site for 

biogeochemical processes, particularly mass and energy 

flows. The size of the basin considered is dependent upon 

the research goals. For geochemical research, relatively 

small basins on homogeneous parent materials are best. 

Hydrologic and geochemical mass-balance techniques are 

applicable to a wide range in size of drainage basins. 

Soils are mapped as geomorphic (morphostratigraphic) units in drainage basins. They are the locus of 

much mass and energy transfer among the atmosphere, 

lithosphere, biosphere, and hydrosphere. On the 10- to 

100-year time scale of contaminant accumulation, they can 

be viewed as complex ion-exchangers or adsorbers of 

metals. 

Soils evolve over geologic time toward steady states 

influenced by climate, vegetation, and parent rock (Birkeland, 1984). The energetics of biological, chemical, and 

mechanical processes operating in the soil are balanced over 

a long time period. Research should include study of 

long-term pedogenic processes, as well as topical studies of 

contaminant loading. 

To facilitate the resampling of representative pedons, 

control sections should be established in drainage basins 

under investigation by the USGS. Undisturbed preserves 

are needed to ensure access to these control sections. 

Ideally, these preserve areas will be at least 1 km2

, be on 

uniform rock types or parent material, and be within 

drainage basins that are part of the USGS National Water 

Quality Assessment Program (NAWQAP). 

RECOMMENDATIONS FOR PROGRAM 

INITIATION 

1. Select sampling areas from basins being studied in 

NAWQAP. 

2. Identify major soil types in each study basin or 

area. 

3. Devise a sampling and analysis scheme that will 

utilize USGS expertise and allow characterization of large 

areas. For example, pick those soils that are typical of the 

study area or those that are considered most sensitive to 

chemical alteration by pollutants (for instance, soils having 

low buffering capacity for acidity in areas of acid-rain 

research). 

4. Establish type sections that can be resampled at 

intervals. Unlike streams or ground waters, which can be 

sampled nondestructively, soil sampling is in itself an 

Weathering Process Research-Pedology and Soil Geochemistry in Drainage Basins 35 
alteration of the natural state of the soil. Care must be taken 

in establishing sites and methods that allow for periodic 

assessment of change. 

5. Use USGS and SCS expertise in the analysis of 

pedons characteristic of soil series (the basic soil mapping 

unit) and in the interpretation of data. A large data base 

exists within SCS files. This should be used where possible. 

REFERENCES CITED 

Birkeland, P.W., 1984, Soils and Geomorphology: New York, 

Oxford University Press, 372 p. 

Markewich, H.W., Lynn, W.C., Pavich, M.J., Johnson, R.G., 

and Meetz, J.C., 1988, Analyses of four inceptisols of 

Holocene age, east-central Alabama: U.S. Geological Survey Bulletin 1589-C, 29 p. 

Markewich, H. W., Pavich, M.J., Mausbach, M.J., Hall, R.L., 

Johnson, R.G., and Hearn, P.P., 1987, Age relations 

between soils and geology in the Coastal Plain of Maryland 

and Virginia: U.S. Geological Survey Bulletin 1589-A, 

34 p. 

Markewich, H. W., Pavich, M.J., Mausbach, M.J., Stuckey, 

B.N., Johnson, R.G., and Gonzalez, Virginia, 1986, Soil 

development and its relation to the ages of morphostratigraphic units in Horry County, South Carolina: U.S. 

Geological Survey Bulletin 1589-B, 61 p. 

McNeal, J.M., Severson, R.C., and Gough, L.P., 1985, The 

occurrence of extractable elements in soils from the northem Great Plains: Soil Science Society of America Journal, 

v. 49, no. 4, p. 873-881. 

Miesch, A.T., 1976, Sampling designs for geochemical surveysSyllabus for short course: U.S. Geological Survey Op~nFile Report 76-772, 138 p. 

Pavich, M.J., 1986, Processes and rates of saprolite production 

and erosion on a foliated granitic rock of the Virginia 

Piedmont, in Colman, S.M., and Dethier, D.P., eds., 

Rates of chemical weathering of rocks and minerals: 

Orlando, Fla., Academic Press, p. 551-590. 

Severson, R.C., and Tidball, R.R., 1979, Spatial variation in total 

element concentration in soil within the northern Great 

Plains coal region: U.S. Geological Survey Professional 

Paper 1134-A, 18 p. 

Soil Survey Staff, 1975, Soil taxonomy: U.S. Department of 

Agriculture, Soil Conservation Service, Agriculture Handbook no. 436, 754 p. 

---1984, Procedure for collecting soil samples and methods of 

analysis for soil survey: U.S. Department of Agriculture, 

Soil Conservation Service, Soil Survey Investigative 

Report No. 1, 68 p. 

Tan, K.H., 1982, Principles of soil chemistry: New York, Marcel 

Dekker, Inc., 267 p. 

36 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
8. The Mode of Occurrence of Extractable Elements 

in Soils from the Northern Great Plains 

By james M. McNeal 

As concerns increase about possible trace-element 

contamination of the environment, it becomes even more 

important to study the manner in which elements occur in 

the natural environment (rocks, soils, sediments, water). 

These studies are particularly useful in determining the 

release, transport, and sorption of elements in the environment. Numerous studies have examined the variation in the 

total-element content of environmental samples, but most 

have not examined the mode of occurrence (the chemical 

form of an element and the mineral phase or phases with 

which the various forms may be associated) of elements in 

the samples. Understanding the mode of occurrence of 

elements in these materials is important because some 

modes of occurrence of an element may not pose a hazard 

for living organisms, whereas some others may be particularly deleterious. In addition, the potential occurrence of 

some environmental problems may be predicted on the basis 

of the mode of occurrence of an element, coupled with 

knowledge of the local geochemical regime. 

In general, two methods are used to examine the 

mode of occurrence of an element. The first method is to 

determine a number of chemical, physical, and mineralogical variables on several related samples. Then, a variety of 

statistical and mathematical tools are used to determine the 

relations between the elements and the chemical, physical, 

and mineralogical variables. These associations are then 

interpreted scientifically according to geochemical principles. The modes of occurrence of an element are interpreted 

accordingly. 

The second method is to treat a sample with a 

carefully predetermined series of chemical extractants. 

Each extractant acts on the residue from the previous 

treatment. The modes of occurrence of an element are then 

interpreted from the concentration of the element in the 

extractant solution and the physical-chemical portion of the 

sample attacked by the extractant. Chao (1984) provided a 

comprehensive review of partial dissolution techniques. 

This paper reviews an example (McNeal and others, 

1985) of how the modes of occurrence of elements in soils 

were determined and shows which modes of occurrence are 

attacked by each of these commonly used soil extractants. 

Studies of this type are necessary for gaining insight into the 

uptake of elements by plants and into the transport of 

elements in the environment. Details of this study were 

reported by McNeal and others (1985). A parallel study 

(Gough and others, 1979) was conducted to determine the 

relation between element uptake by native plants and the 

concentration of elements in soils by using the same 

chemical extractants. 

The soil samples were collected from 21 locations 

from the northern Great Plains (generally eastern Montana, 

western North Dakota, northwestern South Dakota, and 

northeastern Wyoming). The locations represent localities 

of extreme differences (as determined by Q-mode factor 

analysis) in soil composition based on the total-element 

concentration of soils studied by Severson and Tidball 

(1979). 

A large number of variables were determined in this 

study-90 variables for the A horizon and 79 for the C 

horizon. Among the variables determined were totalelement concentrations for Ca, Cu, Fe, K, Mg, Mn, Na, Ni, 

and Zn. The following elements were generally determined 

on the solutions from the six extractants for both soil 

horizons: Ca, Cd, Co, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, and 

Zn. The extractants included are, from the mildest to the 

strongest, Mg(N03h, diethylenetriaminepentaacetic acid 

(DTPA), ethylenediaminetetraacetic acid (EDTA), hydroquinone, ammonium oxalate, and hydrochloric acid (HCl). 

The HCl extraction was not done on the C-horizon soils. 

These extractants were selected because they represent a 

broad range of different kinds of chemical attack and are 

commonly used by soils scientists to investigate the availability of elements in soils to plants. The mineralogy of 

each sample was estimated by using a semiquantitative 

X-ray diffraction technique. Several other commonly determined chemical and physical soil properties also were 

determined. 

R-mode factor analysis was used in this study to 

express the associations among the large number of variables in terms of a smaller number of master variables. The 

associations among the variables are related to the factors 

on the basis of their loadings on each factor. Factor loadings 

The Mode of Occurrence of Extractable Elements in Soils from the Northern Great Plains 37 
Table 8.1. The relative order of importance of factors for all extractable elements (from McNeal and others, 1985) 

[Factors are derived by R-mode factor analysis and varimax rotation in A and C horizons of soils of the northern Great Plains. CEC, cation-exchange 

capacity; (-), loadings are negative] 

Extractable 

element A 

Cadmium . . . . . . . . . . . . Organic = Iron and manganese oxides 

Calcite . . . . . . . . . . . . . . Clay > Organic = Soluble sodium 

Cobalt. . . . . . . . . . . . . . . Iron and manganese oxides > Organic 

Soil horizon 

c 

Iron and manganese oxides > Soluble sodium 

CEC 

Iron and manganese oxides = Clay = CEC 

Copper . . . . . . . . . . . . . . Iron and manganese oxides > Clay = Organic Iron and manganese oxides = Clay = CEC = Iron and 

Iron ................ . 

Lead ............... . 

Magnesium ......... . 

Clay > Iron and manganese oxides 

Organic > Clay > Soluble sodium 

Clay > Soluble sodium = Organic 

manganese 

Manganese .......... . 

Nickel .............. . 

Iron and manganese oxides > Soluble sodium >Clay 

Iron and manganese oxides 

Iron and manganese oxides > Clay 

CEC > Iron and manganese = Clay 

Clay > Iron and manganese oxides (-) 

Iron and manganese oxides > CEC (-) 

Iron and manganese oxides 

Potassium ........... . Organic Clay 

Sodium ............. . Soluble sodium > Clay Soluble sodium 

Zinc ................ . Organic > Iron and manganese oxides = Clay Iron and manganese = Iron and manganese oxides (-) 

= CEC 

are analogous to correlation coefficients. The modes of 

occurrence of the extractable elements in the soils were 

interpreted in geochemical terms on the basis of the magnitude of their loadings on each factor. 

Four factors (organic, clay, iron and manganese 

oxide, and soluble sodium) were found for the A-horizon 

soils, and seven factors (carbonate, clay, cation-exchange 

capacity (CEC), soluble sodium, organic, total iron and 

manganese, and plagioclase) were found for the C-horizon 

soils. About 75 percent of the total variance for each 

horizon was explained by the factor models. The relative 

importance of each factor for each extractable element is 

shown in table 8.1 by soil horizon. 

Each of the extractable major elements (calcium, 

potassium, magnesium, and sodium) generally occurs with 

one factor, regardless of the extractant used. In the A 

horizon, extractable calcium and magnesium are related to 

the clay factor, extractable potassium to the organic factor, 

and extractable sodium to the soluble-sodium factor. In the 

C horizon, extractable calcium is related to the CEC factor, 

extractable potassium and magnesium to the clay factor, 

and extractable sodium to the soluble-sodium factor. These 

results suggest that extractable major elements are water 

soluble and are associated with the constituents that are 

responsible for that factor. 

The extractable trace elements (Cd, Co, Cu, Fe, Mn, 

Ni, Pb, and Zn) for both the A and C horizons are most 

closely associated with iron and manganese oxides, based 

on high loadings with the iron- and manganese-oxide 

factors. In the A horizon, the extractable trace elements also 

have a weak association with the organic factor. The CEC 

and clay factors are also of some importance for trace 

elements extracted from the C-horizon soils. These results 

suggest that iron and manganese oxides are the most 

important residence of these extractable trace elements in 

these soils, underscoring the importance of iron and manganese oxides in controlling the release, transport, and 

sorption of these extractable metals in the environment. 

REFERENCES CITED 

Chao, T.T., 1984, Use of partial dissolution techniques in 

geochemical exploration: Journal of Geochemical Exploration, v. 20, p. 101-135. 

Gough, L.P., Severson, R.C., and McNeal, J.M., 1979, Extractable and total-soil element concentrations favorable for 

native plant growth in the northern Great Plains, in Wali, 

M. K., ed., Ecology and coal resources development, v. 2: 

New York, Pergamon Press, p. 859-869. 

McNeal, J.M., Severson, R.C., and Gough, L.P., 1985, The 

occurrence of extractable elements in soils from the northem Great Plains: Soil Science Society of America Journal, 

v. 49, no. 4, p. 873-881. 

Severson, R.C. and Tidball, R.R., 1979, Spatial variation in total 

element concentration in soil within the northern Great 

Plains coal region: U.S. Geological Survey Professional 

Paper 1134-A. 18 p. 

38 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
9. Uranium-Series Disequilibrium in Quaternary 

Soils-Significance for 222Rn Hazard Assessment 

By Daniel R. Muhs, Charles A. Bush, and John N. Rosholt 

INTRODUCTION 

Radon and its daughter products have been identified 

as major sources of environmental radiation. Estimates of 

the amount of exposure to human beings indicate that this 

radiation may be a leading cause of lung cancer (Evans and 

others, 1981). An important part of studies that assess the 

potential radon hazard is accurate measurement of natural 

radioactivity in the surficial geologic environment or soil 

zone. Sources of surficial geologic radioactivity on a 

regional scale can be measured by laboratory estimates of 

quantities of uranium, thorium, and potassium in typical 

mapped geologic units or by airborne gamma spectrometric 

surveys. In both of these methods, assumptions are made 

about the distribution of uranium and its decay products, 

including 222Rn (fig. 9.1), in soils and surficial geologic 

materials. In this paper, we show that the distribution of 

uranium and its decay products in soils can be complex and 

difficult to predict. 

Uranium has considerable mobility in oxidizing nearsurface environments, where it can occur in the relatively 

soluble (U+6

) state. A portion of the uranium released by 

weathering of some soil constituents may be adsorbed by 

other constituents such as clays, organic matter, manganese 

oxides, and iron oxides (Rosholt and others, 1966; Ames, 

McGarrah, Walker, and Salter, 1982, 1983; Ames, McGarrah, and Walker, 1983a). The degree to which uranium is 

sorbed depends upon solution chemistry, pH, Eh, the type 

and abundance of competing cations and complexing 

agents, surface properties (crystallinity, cation-exchange 

capacity), and the rock-to-water ratio (Langmuir, 1978; 

Giblin and others, 1981; Tsunashima and others, 1981). In 

bicarbonate-rich waters, uranium can migrate as anionic 

carbonate and hydroxide complexes (Langmuir, 1978). 

Thorium, in contrast to uranium, is characterized by 

extreme insolubility in most low-temperature surficial environments (Langmuir and Herman, 1980), and 230Th generated by decay of 234U is predicted to be relatively immobile. 

However, if thorium is introduced into an organic-rich 

environment, some mobility as soluble organic-thorium 

complexes may be possible (Hansen and Huntington, 1969; 

u 

92 

Pa 

91 

Th 

90 

Ac 

89 

Ra 

88 

Fr 

87 

Rn 

86 

2389 

4.47xl0 y 

234 

1.18m 

234 v 

24.ld 

/1 Alpha decay 

Betadecav 

234 

2.48xl05

y 

v 

230 

7.52x 104y 

226 

1.60xl03y 

222 

3.8d 

Figure 9.1. The upper part of the 238U-series 

decay chain, showing nuclides and their halflives discussed in this paper. 

Langmuir and Herman, 1980). 230Th that is adsorbed by 

clays may migrate via physical transport of the clays 

(eluviation and illuviation). 

The mobility of 226Ra is of particular interest because 

it is the immediate parent of 222Rn. There are studies of the 

distribution and mobility of radium in soils, but apparently 

radium generally behaves in a manner similar to that of 

other alkaline earth elements, such as calcium, magnesium, 

strontium, and barium. Studies by Nathwani and Phillips 

( 1979) indicate that 226Ra is adsorbed by clays and organic 

matter; organic matter may sorb more radium than clays in 

Uranium-Series Disequilibrium in Quaternary Soils-Significance for 222Rn Hazard Assessment 39 
the same horizon by as much as a factor of 10. Ames and 

others (1983a,b) conducted experimental studies that 

showed that radium can be adsorbed onto clinoptilolite, 

illite, nontronite, phlogopite, and biotite; sorption efficiency was related to the cation exchange capacity of the 

minerals. These same workers found that, under identical 

conditions, radium sorption is greater than uranium sorption. Ames, McGarrah, Walker, and Salter (1983) found 

that radium is also sorbed by iron oxyhydroxides and that 

sorption is greatest when radium concentrations are high 

and concentrations of competing alkaline earth elements are 

low. 

Over the past few years, we have studied the mobility 

and distribution of 238U, 234U, 230Th, and 226Ra in nearsurface environments by measuring the relative alpha activities of alpha-particle-emitting isotopes in Quaternary soils. 

Determinations of the alpha activities of 238U, 234U, 232Th, 

and 230Th were made by isotope dilution and alpha spectrometric methods (Rosholt, 1984, 1985). The activity of 

226Ra and an independent measurement of 232Th concentration were made by gamma spectrometry (Bunker and Bush, 

1966). 

Our preliminary conclusions are based on analyses of 

124 soil horizons from 17 soil profiles. The soils are from 

Quaternary deposits in California, Nevada, New Mexico, 

Colorado, and the island of Barbados, West Indies. Parent 

materials for the soils are mostly alluvium but also include 

eolian sands and silts, glacial till. and mixtures of volcanic 

ash and airborne dust. The ages of the deposits range from 

middle Pleistocene to Holocene, and climates range from 

arid to humid tropical. 

RESULTS AND DISCUSSION 

Results of radiometric analyses of the 17 soil profiles 

indicate that roughly half of the profiles have 234U/ 238U 

activity ratios of 1.00 or, in other words, show radioactive 

equilibrium. Radioactive equilibrium is defined as a condition where, on the average, there is decay of one parent 

atom for each decay of a daughter atom. In contrast, 

disequilibrium is a condition where the activity of a daughter isotope is greater or less than that of its parent. The other 

half of the profiles show 234U/ 238U ratios greater than unity, 

indicating radioactive disequilibrium, with values ranging 

as high as 1.30 but more commonly in the range of ~34 . 238u 1. 05-1. 20. The frequent excess of - U over 1 ts parent -

in surface waters is well documented and results from the 

preferential leaching of decay-generated 234U atoms from 

mineral surfaces via alpha-recoil mechanisms (see discussions in Rosholt, 1983, 1985). Thus, the 234U/ 238U ratio 

that measures greater than 1.0 in modern soils may simply 

indicate adsorptive uptake of some dissolved uranium from 

coexisting waters passing through the soils. Alternatively, if 

. . f h f. h d h f 238u c23..J.rr,h 234p quantities o t e ust t ree aug ters o 1 , a, 

and 234U) are produced by radioactive decay during the 

passage of uranium-bearing water through the soil, they 

may be preferentially emplaced via a mechanism of recoil 

from the liquid phase onto solid surfaces. In a chronosequence of soils from New Mexico, we found that the 

234U/ 238U alpha activity ratios tend to increase over time; 

that is, soils that are 22 ka and 130 ka had alpha activity 

ratios near equilibrium values (0.98-1.03 and 0.96-1.06, 

respectively), whereas soils that are ~290 ka and ~420 ka 

had activity ratios significantly higher than equilibrium . 1 ) ?34u;238u . (0.98-1.17 and 1.12-1.30, respective y . -- activity ratios as high as 14.0 have been reported for Quaternary 

sediments elsewhere (Szabo, 1982). Study of Tertiary 

zeolites in Utah indicates, however, that, over much longer 

periods of geologic time, preferential displacement of 234U 

by selective leaching may predominate over recoil emplacement or adsorption of 234U (Rosholt, 1980). 

Disequilibrium of 230Th and 226Ra with regard to 

their respective parents is also observed in the soils we 

studied. As a first approximation, we have classified the 

observed disequilibrium into four general categories. The 

first category, seen in two soils from New Mexico and 

Colorado, is characterized by 230Th/ 234U ratios greater than . 2~6Ra/23oTh . 11 1. 0 in most or all of the profile but - - essentta y 

in equilibrium (fig. 9.2). This type of disequilibrium can be 

23oTh/34U 226Ra/23oTh 

0 0 00 q 0 

o · NO N 0--------~------~ -------~------~ 

---t----- ---t-----

1 

I 

el 

.g I 

~I ·g., 

w, 

Figure 9.2. Category 1 disequilibrium in the Berino soil 

(unit CQS) from Eddy County, N. Mex. The soil was 

developed in eolian sediments and has a uraniumtrend age estimate of 360±160 ka (J.N. Rosholt, unpub. 

data). Analytical errors are ±1.6 nercent (1 a) for 23oyh/ 234U and ±8 percent (1 a) for 26Ra/ 23orh. 

40 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
230Thl34u 226Ra/23oTh 23oTh/234u 

0 q 00 q 00 q 00 

Oo No No r.i o 

0 

N ~------~----~~ ~------~----~~ ~------~------~ ~-------r------~ 

.s:; 

Cl) 

~ 

50 Q) 

I Q. 

0 

I c;; 

CJ) 

a: I w 

ti:i 

:::E 

I 

I 

t= 

z 

w 100 (.) 

~ 

~ 

t: 

w 

c 

-t---

I 

I 

I 

I 

I I 

I E I 

I ::::l I "> 

150 I ..2 I < I 

I 

E E ::::l ::::l 

:§ :§ 

31 31 

200 affl affl 

RV1. Nevada 

Figure 9.3. Category 2 disequilibrium in two soil 

profiles from the Nevada Test Site. RV1 consists of 

two superposed soil profiles developed in slope 

wash over alluvium; uranium-trend dates are 

explained by either or both of two processes: leaching of 234U after decay generation of some 230Th or gain of 

particles with unsupported (that is, 234U-depleted) 230Th. 

The added particles could be eolian clays that are leached of 

uranium but that retain the less soluble 230Th daughter. 

A second category of disequilibrium is a variation of 

the first, where there is again a 230Th/ 234U excess in surface 

horizons, but a 230Th/ 234U deficiency at lower depths. Soils 

from New Mexico and Nevada illustrate this phenomenon, 

and we suggest that this phenomenon represents leaching of 

uranium, particularly 234U, from upper parts of the profiles 

and its accumulation at lower depths (fig. 9.3). 

Greater complexity is illustrated by the third category 

of disequilibrium in which both 230Th/ 234U excesses and 226Ra! 230Th excesses are found in most horizons. Soils 

from Nevada and New Mexico provide typical examples of 

this category, and soils from Barbados illustrate an extreme 

example of 230Th/ 234U excess (fig. 9.4). In the case of 

Barbados, the dominant process of 230Th/ 234U excess is 

almost certainly uranium leaching via intense tropical 

weathering, because soil parent materials (volcanic ash 

.s:; 

Cl) 

ca 

~ 

Q) 

c. 

0 

c;; 

E 

::::l "> .2 

< 

I 

I 

I 

I I 

I I 

I I 

I I 

I 

§I e' .:!1 

:§I :el 31 31 

affl afft 

TSV-307. Nevada 

31 ±10 ka and 310±40 ka, respectively (Rosholt and 

others, 1985). Unit TSV-307 is developed in alluvium 

and has a uranium-trend date of 38±10 ka. Analytical 

errors are the same as those given in figure 9.2. 

from St. Vincent and airborne dust from Africa) have 230Th/ 234U ratios that are 1.0 (equilibrium) or are actually 

less than unity (Rydell and Prospero, 1972; Muhs and 

others, unpub. data). In Nevada and New Mexico, intense 

chemical weathering is less likely, and we suggest that the 230Th excesses are most likely due to eolian input of 

airborne clays and silts having unsupported 230Th. Interestingly, the excess of 226Ra over its parent 230Th suggests 

that, in New Mexico and Nevada, two eolian sources may 

be involved, one having unsupported 230Th and one having 

unsupported 226Ra. On Barbados, we lack 226Ra data for the 

soil parent materials, but on the basis of 222Rn measurements reported by Carlson and Prospero (1969), we suspect 

that unsupported 226Ra is present in the airborne dust from 

Africa. For all soils of the third category, at least some 

processes have taken place during the Holocene, because 226Ra is not yet in radioactive equilibrium with 230Th. 

The fourth category of disequilibrium is a simplified 

version of the third category. 226Ra/230Th values are again 

greater than unity, but 230ThP34U ratios are at equilibrium 

values or are even less than unity. Certain soils from New 

Uranium-Series Disequilibrium in Quaternary Soils-Significance for 222Rn Hazard Assessment 41 
23oTh/234u 226Ra/23oTh 23oTh/34U 

0 q 00 q 0 0 

0 0 N 0 N 0 - N (") 'It It) CD ..... 0 

0 

C'oi 

------------------ ~-------r-------- ~------~------~ 

20 

U) 

a: 

w 

tu 

:E 

i= 

z 

w 

u 40 

~ 

~ 

t: 

w 

a 

60 

E E -~I ::I 

·c 

~I ;g 

g., ·s 

affl 

80 WI I 

UT-3. New Mexico 

Figure 9.4. Category 3 disequilibrium in soil profiles 

developed in lzaac's Ranch alluvium (UT-3), southern New Mexico (Gile and Grossman, 1979), and 

on the Rendezvous Hill coral terrace (BAR-3A), 

Mexico and the San Joaquin Valley of California fall into 

this category. We suspect that the observed 226Ra!230Th 

excesses may be explained by Holocene additions of unsupported 226Ra via airborne silts and clays, but the mechanism 

by which the 226Ra excess is produced has not been 

identified. Radium mobility in arid environments resulting 

in disequilibrium on eolian particles has been suggested by 

other investigators (Hirose and Sugimura, 1984). Alternatively, 226Ra may enter the soils in waters that pass through 

the soils subsequent to parent material deposition and soil 

formation. 

CONCLUSIONS 

The observations we have summarized here suggest 

that radioactive disequilibrium of the uranium series is a 

common occurrence in soils of Quaternary age. Excesses of 234U over its parent 238U are observed in about half of the 

soils that we examined and are probably due to adsorption 

of dissolved uranium and the daughter-emplacement proI 

I 

I 

E El 

.2 -~I 

~ ~I ·s 61 $1 I w, 

BAR-3A. Barbados 

Barbados. Ages are 22±15 ka (uranium-trend) and 

about 125 ka (uranium-series), respectively. Analytical errors are similar to those given in figure 9.2. 

cess as dissolved uranium and daughters pass through the 

soil profiles. Other indications of disequilibrium such as 

alpha activity of 230ThP34U greater than 1.0 may be 

explained by either eolian additions of unsupported 230Th 

or, in the case of tropical environments, loss of uranium 

through weathering processes. Excesses of 226Ra over its 

parent 230Th may be due to additions of airborne dust that 

have unsupported 226Ra. Other studies have documented 

that certain of our study areas, such as the Rio Grande 

Valley of New Mexico, the San Joaquin Valley of California, and Barbados, are localities that receive significant 

quantities of airborne dust (Gile and Grossman, 1979; 

Prospero, 1981; Wilshire and others, 1981; Muhs and 

others, 1987). Similarity of uranium-series disequilibrium 

in the Nevada soils indicates that eolian additions may be 

important in that locality as well. 

Our observations have significance for 222Rn hazardassessment studies. Some preliminary assessments have 

been made by using airborne gamma spectrometric data and 

geologic maps. In situations where soils are derived largely 

from the underlying consolidated rocks, there is a good 

42 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
match between the derived radioactivity maps and the 

uranium, thorium, and potassium contents of the bedrock 

units (Pitkin, 1968; Schwarzer and others, 1972; Schwarzer 

and Adams, 1973). However, because airborne surveys 

measure only the radioactivity of the upper 50 em or less of 

the soils (Duval and others, 1971), deeper horizons that 

have high activities of 230Th and 226Ra (and thus sources for 222Rn), such as we have observed, are not measured. In 

areas where 230Th and 226Ra are found on eolian particles, 

the radioactivity of the upper soil horizons may be unrelated 

to the uranium content of the underlying rocks. Thus, our 

observations of uranium-series disequilibrium in soils suggest that both geologic maps and airborne surveys provide 

only general indicators of the radioactivity of soils. 

REFERENCES CITED 

Ames, L.L., McGarrah, J.E., and Walker, B.A., 1983a, Sorption 

of uranium and radium by biotite, muscovite, and phlogopite: Clays and Clay Minerals, v. 31, no. 5, p. 343-351. 

---1983b, Sorption of trace constituents from aqueous solutions onto secondary minerals; II, Radium: Clays and Clay 

Minerals, v. 31, no. 5, p. 335-342. 

Ames, L.L., McGarrah, J.E., Walker, B.A., and Salter, P.F., 

1982, Sorption of uranium and cesium by Hanford basalts 

and associated secondary smectite: Chemical Geology, 

v. 35, no. 3-4, p. 205-225. 

---1983, Uranium and radium sorption on amorphous ferric 

oxyhydroxide: Chemical Geology, v. 40, no. 1-2, 

p. 135-148. 

Bunker, C.M., and Bush, C.A., 1966, Uranium, thorium, and 

radium analyses by gamma-ray spectrometry (0.184-0.352 

million electron volts), in Geological Survey Research, 

1966, chap. B: U.S. Geological Survey Professional Paper 

550-B, p. B176--B181. 

Carlson, T.N., and Prospero, J.M., 1969, Radon-222 in the trade 

winds of the tropical North Atlantic and its relationship to 

airborne dust transport from Africa: Eos (Transactions, 

American Geophysical Union), v. 50, p. 176. 

Duval, J.S., Cook, B., and Adams, J.A.S., 1971, Circle of 

investigation of an airborne gamma-ray spectrometer: Journal of Geophysical Research, v. 76, p. 8466-8470. 

Evans, R.D., Harley, J.H., Jacobi, W., McLean, A.S., Mills, 

W.A., and Stewart, C.G., 1981, Estimate of risk from 

environmental exposure to radon-222 and its decay products: Nature, v. 290, no. 5802, p. 98-100. 

Giblin, A.M., Batts, B.D., and Swaine, D.J., 1981, Laboratory 

simulation studies of uranium mobility in natural waters: 

Geochimica et Cosmochimica Acta, v. 45, no. 5, 

p. 699-709. 

Gile, L. H. , and Grossman, R. B. , 1979, The Desert Project Soil 

Monograph: Washington, D.C., U.S. Department of Agriculture, Soil Conservation Service, 984 p. 

Hansen, R.O., and Huntington, G.L., 1969, Thorium movements 

in morainal soils of the High Sierra, California: Soil 

Science, v. 108, no. 4, p. 257-265. 

Hirose, K., and Sugimura, Y., 1984, Excess 228Th in the airborne 

dust: An indicator of continental dust from the East Asian 

deserts: Earth and Planetary Science Letters, v. 270, 

p. 11-114. 

Langmuir, Donald, 1978, Uranium solution-Mineral equilibria 

at low temperatures with applications to sedimentary ore 

deposits: Geochimica et Cosmochimica Acta, v. 42, no. 

6B, p. 547-570. 

Langmuir, Donald, and Herman, J.S., 1980, The mobility of 

thorium in natural waters at low temperatures: Geochimica 

et Cosmochimica Acta, v. 44, no. 11, p. 1753-1766. 

Muhs, D.R., Crittenden, R.C., Rosholt, J.N., Bush, C.A., and 

Stewart, K.C., 1987, Genesis of marine terrace soils, 

Barbados, West Indies-Evidence from mineralogy and 

geochemistry: Earth Surface Processes and Landforms, 

V. 12, p. 605-618. 

Nathwani, J.S., and Phillips, C.R., 1979, Adsorption of 226Ra by 

soils (I): Chemosphere, v. 8, p. 285-291. 

Pitkin, J.A., 1968, Airborne measurements of terrestrial radioactivity as an aid to geologic mapping: U.S. Geological 

Survey Professional Paper 516--F, 29 p. 

Prospero, J .M., 1981, Eolian transport to the world ocean, in 

Emiliani, Cesare, ed., The oceanic lithosphere, v. 7 ofThe 

sea: New York, John Wiley and Sons, p. 801-874. 

Rosholt, J.N., 1980, Uranium and thorium disequilibrium in 

zeolitically altered rock: Nuclear Technology, v. 51, 

p. 143-146. 

---1983, Isotopic composition of uranium and thorium in 

crystalline rocks: Journal of Geophysical Research, B, 

v. 88, no. 9, p. 7315-7330. 

---1984, Radioisotope dilution analyses of geological samples 

using 236U and 229Th: Nuclear Instruments and Methods in 

Physics Research, v. 223, no. 2-3, p. 572-576. 

---1985, Uranium-trend systematics for dating Quaternary 

sediments: U.S. Geological Survey Open-File Report 

85-298, 35 p. 

Rosholt, J.N., Bush, C.A., Carr, W.J., Hoover, D.L., Swadley, 

WC, and Dooley, J.R., Jr., 1985, Uranium-trend dating of 

Quaternary deposits in the Nevada Test Site area, Nevada 

and California: U.S. Geological Survey Open-File Report 

85-540, 72 p. 

Rosholt, J.N., Doe, B.R., and Tatsumoto, M., 1966, Evolution of 

the isotopic composition of uranium and thorium in soil 

profiles: Geological Society of America Bulletin, v. 77, no. 

9, p. 987-1003. 

Rydell, H.S., and Prospero, J.M., 1972, Uranium and thorium 

concentrations in wind-borne Saharan dust over the western 

equatorial north Atlantic Ocean: Earth and Planetary Science Letter~. v. 14, p. 397-402. 

Schwarzer, T.F., and Adams, J.A.S., 1973, Rock and soil 

discrimination by low altitude airborne gamma-ray spectrometry in Payne County, Oklahoma: Economic Geology, 

v. 68, no. 8, p. 1297-1312. 

Schwarzer, T.F., Cook, B., and Adams, J.A.S., 1972, Low 

altitude gamma-spectrometric surveys from helicopters in 

Puerto Rico as an example of the remote sensing of 

thorium, uranium, and potassium in soils and rocks: 

Remote Sensing of Environment, v. 2, p. 83-94. 

Uranium-Series Disequilibrium in Quaternary Soils-Significance for 222Rn Hazard Assessment 43 
Szabo, B.J., 1982, Extreme fractionation of 234U/ 238U and 230Th! 234U in spring waters, sediments, and fossils at the 

Pomme de Terre Valley, southwestern Missouri: Geochimica et Cosmochimica Acta, v. 46, no. 9, p. 1675-1679. 

Tsunashima, A., Brindley, G.W., and Bastovanov, Marija, 1981, 

Adsorption of uranium from solutions by montmorillonite-Compositions and properties of uranyl montmorillonites: Clays and Clay Minerals, v. 29, no. 1 , 

p. 10-16. 

Wilshire, H.G., Nakata, J.K., and Hallet, Bernard, 1981, Field 

observations of the December 1977 wind storm, San 

Joaquin Valley, California, in Pewe, T.L., ed., Desert 

dust-Origin, characteristics, and effects on man: Geological Society of America Special Paper 186, p. 233-251. 

44 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
1 0. Biogeochemical Baselines and the Importance 

of Species, Plant Parts, and Season-The U.S. 

Geological Survey's Studies of Big Sagebrush 

in the West 

By james A. Erdman 

Unlike nonliving sample media, such as rocks or 

soils, the effects of species (or even subspecies and cultivars), plant parts, and season can seriously flaw attempts to 

develop element-compositional baselines for plants. Such 

effects must be considered in designing baseline studies that 

include vegetation. The U.S. Geological Survey's (USGS) 

experience with big sagebrush (Artemisia tridentata Nutt.) 

underscores some of the success, as well as problems, 

encountered in the field of environmental geochemistry. 

The sole basis for selecting sagebrush is simple-the 

sagebrush-grass vegetation makes up one of the largest 

range ecosystems in the Western United States. It extends 

over much of Utah, Nevada, southern Idaho, eastern 

Oregon, western Montana, and Colorado, as well as smaller 

areas in Washington, California, Arizona, and New Mexico. 

REGIONAL BASELINE STUDIES 

The first efforts by the USGS to establish regionalscale ·baselines for native plants and cultivated crops were 

conducted as part of a cooperative study with the Environmental Health Surveillance Project at the University of 

Missouri, Columbia (Erdman and others, 1976a,b). Following that work, efforts were focused on possible geochemical 

changes that might result from the reclamation of surface 

coal mines in the West. To assess such changes, baselines 

had to be developed for regions that might be affected. 

Initial attempts to establish baselines for big sagebrush 

began in the northern Great Plains lignite province, in 

particular the Powder River Basin (Tidball and others, 

1974; Connor and others, 1976), and used nested barbell or 

gridded sampling designs. 

The most extensive baseline study of big sagebrush 

involved the collection and analysis of samples from 190 

sites in 8 physiographic provinces of the West (see figure 

3.3 in Shacklette, this volume). In this study, Gough and 

Erdman (1983) used an eight-level analysis-of-variance 

design to "take into account the predominant scales of 

geochemical variability inherent in nature" (Connor and 

others, 1976, p. 49). Such an account is a mandatory 

requirement of any attempt to establish geochemical baselines. 

The general conclusions of the three baseline studies 

of big sagebrush mentioned above are that baselines are best 

expressed as ranges of element concentrations, such as the 

central 95-percent range, a definition of baseline first 

proposed by Tidball and Ebens (1976). Results of the 

analysis-of-variance sampling designs clearly showed the 

importance of small-scale (local) element variation in sagebrush. Estimates of this variation indicated that samples of 

sagebrush collected at opposite ends of the regions or 

physiographic provinces generally differed little more than 

samples taken only several miles apart. Mapping the distribution of elements would have been useless for the most 

part; considerably more effort would have been needed, 

including perhaps resampling the region, to ensure stable 

geochemical maps. 

One result of the study by Gough and Erdman (1983) 

was the evidence of possible uranium mineralization in 

southwestern Idaho (Erdman and Harrach, 1981). In 

response to that paper, Diebold and McGrath (1985) conducted a detailed study of the anomaly and, through 

hydroponic experiments, investigated the effect of groundwater chemistry on the uptake of uranium by big sagebrush. 

TOPICAL STUDIES 

Big sagebrush is a highly polymorphic species. Three 

subspecies (ssp. tridentata, wyomingensis, and vaseyana) are 

generally recognized. Because identification of these subspecies in the field is difficult, even for brushland taxonomists, Gough and Erdman (1983) considered big sagebrush 

as a single taxonomic entity. Results of a uniform gardenBiogeochemical Baselines and the Importance of Species, Plant Parts, and Season 45 
plot study conducted in 1978 of the three recognized 

subspecies (J.A. Erdman, unpub. data) indicated that significant differences in concentrations of some elements in 

leaf samples do exist. Yet they seem to be minor compared 

with those differences observed among the provinces. 

Nevertheless, such genetic effects need to be assessed in 

any baseline study. 

Seasonal effects may be equally important. Gough 

and Erdman ( 1980) sampled a stand of Wyoming big 

sagebrush over a period of 1 year and found that seasonal 

changes in the concentrations of the major elements reflect 

phenological events that alter the proportion of leaf-to-stem 

tissue in the samples. In general, the element composition 

of younger tissue fluctuated more, had higher concentrations, and showed greater differences among seasons than 

did the older material. These results underscore the importance not only of season, but also of plant part on element 

concentrations. Erdman and Olson (1985) reported that, in 

the Soviet Union, where sagebrush has seen considerable 

use in mineral prospecting, sampling of Artemisia (wormwood) is conducted in the spring when the gold concentrations in ash are about 10 times the levels observed in the fall 

(80-85 parts per million (ppm) in May and only 4-8 ppm in 

October). 

In summary, baselines for element concentrations in 

plants are attainable, but sampling should be completed in a 

relatively short period of a single season and certainly not 

extended from one year to the next. Unlike efforts to 

achieve such data for rocks and soils, considerations of the 

effects of genetics, parts, and season are mandatory for 

plants. 

REFERENCES CITED 

Connor, J.J., Keith, J.R., and Anderson, B.M., 1976, Tracemetal variation in soils and sagebrush in the Powder River 

Basin, Wyoming and Montana: U.S. Geological Survey 

Journal of Research, v. 4, no. 1, p. 49-59. 

Diebold, F.E., and McGrath, Steve, 1985, Investigation of 

Artemisia tridentata as a biogeochemical uranium indicator: Journal of Geochemical Exploration, v. 23, p. 1-12. 

Erdman, J.A., and Harrach, G.H., 1981, Uranium in big sagebrush from Western U.S. and evidence of possible mineralization in the Owyhee Mountains of Idaho: Journal of 

Geochemical Exploration, v. 14, no. 1, p. 83-94. 

Erdman, J.A., and Olson, J.C., 1985, The use of plants in 

prospecting for gold-A brief overview with a selected 

bibliography and topic index: Journal of Geochemical 

Exploration, v. 24, no. 3, p. 281-304. 

Erdman, J.A., Shacklette, H.T., and Keith, J.R., 1976a, Elemental composition of selected native plants and associated 

soils from major vegetation-type areas in Missouri: U.S. 

Geological Survey Professional Paper 954-C, 87 p. 

---1976b, Elemental composition of corn grains, soybean 

seeds, pasture grasses, and associated soils from selected 

areas in Missouri: U.S. Geological Survey Professional 

Paper 954-D, 23 p. 

Gough, L.P., and Erdman, J.A., 1980, Seasonal differences in the 

element content of Wyoming big sagebrush: Journal of 

Range Management, v. 33, no. 5, p. 374-378. 

---1983, Baseline elemental concentrations for big sagebrush 

from Western U.S.A.: Journal of Range Management, 

v. 36, no. 6, p. 718-722. 

Tidball, R.R., and Ebens, R.J., 1976, Regional geochemical 

baselines in soils of the Powder River Basin, MontanaWyoming, in Laudon, R.B., ed., Geology and energy 

resources of the Powder River Basin, Wyoming Geological 

Association 28th annual field conference guidebook: 

Casper, Wyoming Geological Association, p. 299-310. 

Tidball, R.R., Erdman, J.A., and Ebens, R.J., 1974, Geochemical baselines for sagebrush and soil, Powder River Basin, 

Montana-Wyoming, in Geochemical survey of the western 

coal regions, first annual progress report, July 1974: U.S. 

Geological Survey Open-File Report 74-250, p. 6-13. 

46 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
11. Vegetation Studies in the Northern Great Plains 

By Larry P. Gough 

INTRODUCTION 

Between 1974 and 1978, the U.S. Geological Survey 

(USGS) was actively involved in the environmental 

geochemical and biogeochemical characterization of the 

northern Great Plains as it related to present and projected 

surface-coal mining activities. Regulations governing the 

reclamation of mined land require that the land be returned 

to its former use, which, in the northern Great Plains, is 

mainly pasture and small-grain production. Therefore, an 

assessment of the impact of surface mining in this region 

must include a consideration of the possible effects on the 

growth and chemical characteristics of both agricultural 

species, utilized by man, and native plant species, utilized 

by grazing animals. As part of the USGS Energy Lands 

Program, biogeochemical studies in this region focused on 

three broad topics: (1) chemical-element characterization of 

small grains; (2) chemical-element characterization of 

native species and of their relation to the availability of 

major and minor nutrient elements and environmentally 

important metals in soils at geochemically diverse sites; and 

(3) comparison of the chemistry of native and introduced 

pasture species growing in both rehabilitated mine sites and 

adjacent undisturbed sites, as well as the relation of these 

species to soil chemistry. 

NATIVE-SITE METAL AVAILABILITY AND 

UPTAKE BY PLANTS 

Agricultural Species Studies 

A hierarchical-nested analysis of variance (ANOV) 

design was used in the sampling of hard-red spring and 

hard-red winter wheat grains on lands undisturbed by 

surface mining throughout the northern Great Plains, 

including the southern edge of Saskatchewan, Canada. This 

design enabled the partitioning of the variability in the 

elemental concentration of wheat among various geographic 

scales (Erdman and Gough, 1979). The regional variability 

information was used as an aid in the estimation of 

biogeochemical baseline values, as defined by Tidball and 

Ebens ( 1976). These baseline data then were used to 

compare the chemistry of wheat grown on topsoiled spoil 

material among several surface-coal mines. 

Native Species Studies 

Twenty-one study locations in the northern Great 

Plains were identified on the basis of their geochemical 

variability (fig. 11.1) (Severson and others, 1977; Gough 

and others, 1979). Material sampled at each location 

included western wheatgrass, silver sagebrush, total aboveground plant biomass, and A and C soil horizons. Both total 

and extractable element levels in soil were examined. 

Bioavailability measures.-Total element levels in 

plants can be considered as representing the bioavailable 

fraction of the soil. In addition, biomass samples measure 

the biogeochemical load in the vegetation. Biomass sampling is a means of studying the bioavailable metal levels of 

a region and not just of a species. As examples, biomass 

ranged from 200 kg/ha at a heavily grazed Montana site to 

1 ,800 kg/ha at a Wyoming site and resulted in load 

estimates of copper, 0.3-2.2; iron, 12-410; and zinc, 7-56 

g/ha. 

Native-soil and plant-element relations. -Metal concentrations in A and C soil horizons showed large geochemical variability between sites in both the total digestions and 

in the extractions. Samples of herbage, however, showed 

very little variability. A stepwise multiple regression analysis was used to study the relation between physical and 

chemical soil properties and metal uptake by plants (Gough 

and others, 1980). This procedure resulted in prediction 

equations that related the concentration of a given element 

in plants to selected physical and chemical soil properties. 

The resulting prediction equations showed that 

diethylenetriamine-pentaacetic acid (DTPA) extractable 

levels were more important as a measure of the elementavailable soil fraction than ethylenediaminetetraacetic acid 

(EDTA) levels. 

The parameter pH appeared in more of the regression 

equations than any other independent variable, and the 

regression coefficient was always positive. The standard 

partial regression coefficient ratios showed that, in those 

equations where pH occurred with other significant 

independent variables, pH was always the most 

Vegetation Studies in the Northern Great Plains 47 
Figure 11.1. Sampling locations (dots) within the area of 

strippable coal deposits, northern Great Plains. 

important. In general, copper, iron, and zinc concentrations 

in native plants increased with increasing pH of the A 

horizon (pH range of 6.2-8.2). Further, as pH of the A 

horizon increased, so did the relative uptake of these three 

metals. It is theorized that, below a pH of about 7. 5, these 

metals exist mainly in noncarbonate forms but that, above a 

pH of 7.5, they also occur as metal carbonates. Therefore, 

a slight reduction in pH in the rhizosphere (caused by acid 

production at the root surface) could easily release metals 

from these carbonates in ionic forms readily available for 

assimilation by wheatgrass. These data suggest that native 

plants in the northern Great Plains tend to assimilate higher 

concentrations of copper, iron, and zinc when growing in 

A-horizon carbonate soils that have a pH above 7. 5. 

MINE-SITE METAL UPTAKE BY PLANTS 

Mine-soil and plant-element relations.-A map of 

mines studied is given by Severson (fig. 24.1, this volume). 

A general lack of significant relations was found between 

the DTPA-extractable metal levels measured in mine soils 

and metals in plants. As with the native site studies, this 

lack suggests that a simple model is not adequate for 

estimating element uptake by plants. Organic-matter content and pH of mine soils, individually or in combination 

with DTPA-extractable metals, do not adequately model 

plant-element uptake from the mine soils in this study. 

Positive relations between the relative uptake of DTPAextractable metals in mine soils and pH are the same as 

those reported in the previous section for native plants 

growing on undisturbed soils. 

Biogeochemical comparisons among mines.-Element concentrations were determined in samples of crested, 

slender, and intermediate wheatgrass, alfalfa, and fourwing 

saltbush (Gough and Severson, 1983). Differences in element concentrations of these materials were assumed to 

reflect variability in the mine environment, specifically 

cover soil and spoil mineralogy, lithology, and bioavailability. Comparisons of element levels were made among 

species from different mines and among species within 

mines. Mines were then ranked according to similar biogeochemical element amounts. Absolute concentrations of 

environmentally important elements were examined for 

possible phytotoxic levels. As an example, extremely high 

boron concentrations in saltbush at a Wyoming mine 

(110-610 ppm, dry material) reflected phytotoxic levels in 

the mine soils. 

RECOMMENDATIONS 

Studies are needed to develop a soil extractant that 

makes use of new information on the probable major mode 

of metal occurrence in soils and on the apparent role of 

metal carbonates as a prime reservoir for the direct assimilation of metal by plants. Investigations on mineral weathering as it relates to element dissolution would also help in 

the formulation of a new extractant. Although our work has 

resulted in prediction equations for metal uptake by plants 

(using various soil-chemical and physical parameters on 

both native and mine-disturbed sites), a satisfactory level of 

precision for these equations, compared to what might be 

obtained by a new extractant, has not yet been achieved. 

Additional work is needed to define baseline element 

concentrations in plant species used in mine rehabilitation. 

The U.S. Geological Survey is one of the few organizations 

that has approached such studies on a regional scale. 

REFERENCES CITED 

Erdman, J.A., and Gough, L.P., 1979, Mineral composition of 

wheat from coal-mine spoils and farms in the northern 

Great Plains, in Wali, M.K., ed., Ecology and coal 

resource development: New York, Pergamon Press, 

p. 878-886. 

Gough, L.P., McNeal, J.M., and Severson, R.C., 1980, Predicting native plant copper, iron, manganese, and zinc levels 

using DTP A and EDT A soil extractants, northern Great 

Plains: Soil Science of America Journal, v. 44, 

p. 1030-1036. 

48 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Gough, L.P., and Severson, R.C., 1983, Rehabilitation materials 

from surface-coal mines in Western U.S.A., II, Biogeochemistry of wheatgrass, alfalfa and fourwing saltbush: 

Reclamation and Revegetation Research, v. 2, p. 103-122. 

Gough, L.P., Severson, R.C., and McNeal, J.M., 1979, Extractable and total soil-element concentrations favorable for 

native plant growth in the northern Great Plains, in Wali, 

M.K., ed., Ecology and coal resource development: New 

York, Pergamon Press, p. 859-869. 

Severson, R.C., Gough, L.P., and McNeal, J.M., 1977, Availability of elements in soil to native plants, northern Great 

Plains: U.S. Geological Survey Open-File Report 77-847, 

93 p. 

Tidball, R.R., and Ebens, R.J., 1976, Regional geochemical 

baselines in soils of the Powder River Basin, MontanaWyoming, in Laudon, R.B., ed., Geology and energy 

resources of the Powder River Basin, Wyoming Geological 

Association, 28th annual field conference guidebook: 

Casper, Wyoming Geological Association, p. 299-310. 

Vegetation Studies in the Northern Great Plains 49 

12. Remote Sensing of Vegetative Responses to the 

Environment 

By Nancy Milton 

INTRODUCTION 

Studies of geology and soils can be hampered by a 

vegetation canopy that obscures outcrops and covers soils 

with a thick layer of plant litter and humus. Biogeochemical 

and geobotanical techniques, however, have proved to be 

successful in deriving information about rocks and soil from 

vegetation characteristics. For studies requiring a broad 

regional perspective, and in areas where sampling is difficult, remote sensing of plants can provide a rapid, inexpensive means of assessing the chemical and physical environment in which the plants are growing. 

PLANT RESPONSES TO ENVIRONMENT 

The vegetation growing in a given area is adapted to 

the conditions of water, soil, and air that control growth. 

The response of the vegetation to anomalous conditions, 

such as the introduction of toxic elements (whether natural 

or cultural), can result in macroscopic or spectroscopic 

changes. For example, on a macroscopic scale, the growth 

of the plant can be stunted (dwarfism or decreased biomass) 

or enhanced (gigantism or increased biomass); the timing of 

flowering, fruiting, or senescence can be altered (phenologic changes); or the anomalous area may be invaded by 

different species better adapted to the presence of toxic 

levels of specific elements (such as the endemic flora 

associated with copper or the vegetation adapted to high 

magnesium-to-calcium ratios, or high nickel or chromium 

on ultramafics). Other responses are spectroscopic in scale 

and are not readily discernible. The uptake of toxic elements by plants can result in subtle changes in the spectral 

reflectance of leaves in the visible and near-infrared regions 

of the electromagnetic spectrum. 

REMOTE SENSING OF VEGETATION 

The vegetation responses that are visible to the eye 

frequently occur on a scale that allows remote detection by 

low-resolution satellite sensors. Changes in species distribution due to biogeochemical anomalies in the soil have 

been recorded in Landsat multispectral scanner (MSS) data. 

Phenologic changes, such as delayed leaf flush and early 

senescence in deciduous forests growing on mineralized 

soils, have been detected in Landsat Thematic Mapper 

(TM) data. 

The spectral responses of vegetation that are not 

always visible to the eye can be detected by high-resolution 

sensors, presently limited to airborne platforms. Spectral 

responses of interest in geobotany occur in the region of the 

EM spectrum from 0.4 to 2.5 1-1m (fig. 12.1). These spectra 

of red maple and loblolly pine were recorded on a laboratory Beckman 5240 spectrophotometer, which uses an 

integrating sphere and a barium sulfate standard. Resolution 

is 1 nm between 0.4 and 0.8 1-1m and between 0.8 and 2.5 

IJ.m. 

Low reflectance in the visible region (0.4--0. 7 ~J.m) 

results from absorption by plant pigments, notably xanthophylls and carotenoids in the blue and chlorophylls in the 

red region. Plants reflect about 40 to 60 percent of incoming 

radiation in the very near infrared (0. 7-1.0 ~J.m); this 

reflectance helps to prevent overheating. Reflectance in this 

region is controlled by scattering at interfaces between cell 

walls, air, and water. In the shortwave infrared (1.0-2.5 

1-1m), reflectance decreases because of the presence of water 

to a low of about 5 percent. 

The presence of toxic elements in the plants can result 

in changes in various regions of the plant spectrum. Of 

particular importance is the shift in the longwave edge of 

the chlorophyll absorption band centered near 0.68 1-1m 

toward shorter wavelengths. This shift is illustrated in 

figure 12.2, especially in the first derivative spectrum, 

which shows the change in wavelength position of the 

inflection point. The shift is variously reported in the 

literature to range from 6 to 20 nm in extent, so that 

high-resolution instruments are required to detect it. Field 

studies using airborne radiometer data have verified that 

such a shift takes place in the vegetation growing over 

geochemically anomalous soils in Montana, North Carolina, and Vermont. 

Remote Sensing of Vegetative Responses to the Environment 51 
I PIGMENT I CELLULAR I I f-"-ABSORPTION~ SCATTERING-~~MIEE------ LEAF WATER ABSORPTION----.....;;a.:iill 

70r-----------------~----~ r-----~----------------------------------------------; 

60 

;::: 50 z 

w 

(.) 

0:: 

~ 40 

w 

(.) 

z 

<t 30 .,_ 

(.) 

w 

_. 

lL 

w 20 Q: 

10 

o.s 0.8 o.e r.o 

WAVELENGTH 

\ 

\ 

' ' ' ' ' \ I 

\ I 

\.J 

1.5 

(MICROMETERS) 

Red Maple 

Loblolly Pine 

,.... ...... 

/ ' I \ 

I \ 

I ' I \ 

\ 

' 

2.0 

Figure 12.1. Spectral reflectance measurements of greenhouse-grown red maple and loblolly pine trees. 

In summary, the remote-sensing capability exists at 

several levels of resolution to monitor plant responses to 

environmental conditions, such as the presence of geochemical anomalies in the soil. 

1-

z 

w 

(.) 

0:: 

w 

~ 

w 

(.) 

z 

~ (.) 

w 

....J 

I.a.. 

w 

a::: 

30 

20 

10 

0 

-10 

A 

50 

HOST A VENTRICOSA 

40 

30 -coNTROL 

20 

10 

o~-~-~-~--~---~---~-~~~ 

0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 

B WAVELENGTH (MICROMETERS) 

Figure 12.2. A, Spectral reflectance curves of NiS04 -

stressed and control hosta plants. 8, First-derivative 

spectra. 

52 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
13. Cooperative Studies by the U.S. Geological 

Survey and the U.S. National Park Service in 

Environmental Biogeochemistry 

By Larry P. Gough, R.C. Severson, and Larry L. jackson 

INTRODUCTION 

In July 1983, the U.S. Geological Survey (USGS) 

and the U.S. National Park Service (NPS) signed an 

interagency agreement for joint investigations of suspected 

biogeochemical problems originating from airborne contaminants in and near selected national park units (fig. 

13.1). The NPS is responsible for protecting the air quality 

of park regions from significant deterioration. The USGS 

and the NPS are assessing the effect of known contamination sources on sulfur and trace-metal concentrations in 

plants, soils, and other natural materials (Gough, Peard, 

and others, 1985). Results of these studies are used in 

air-quality management decisions for the park units and for 

areas adjacent to them. 

Study designs and specific objectives differ from one 

region to another and include (1) the use of lichens (or other 

"air plants") or vascular plant species as biomonitors of 

possible phytotoxic conditions, (2) the use of native materials to determine the region of measurable influence of a 

suspected point source of sulfur and (or) metal contamination, and (3) the establishment of baseline biogeochemical 

and geochemical levels so that the magnitude of chemical 

changes with time can be monitored. 

SUMMARY OF COMPLETED STUDIES 

Theodore Roosevelt National Park.-Investigations 

at Theodore Roosevelt National Park (TRNP), N. Dak., 

were divided into three parts: study 1, the comparison of 

lichen sample-preparation techniques and the development 

of a routine analytical method for the determination of 

sulfur in plant materials (Jackson and others, 1985); study 

2, the definition of element-concentration baselines for 

selected plants and soils within TRNP; and study 3, the 

assessment of the influence of emissions from a natural-gas 

processing facility near TRNP on element levels of selected 

plants and soils (Gough, Peard, and others, 1985). 

Samples of green ash, western wheatgrass, big sagebrush, a tree lichen, and soils were collected to estimate the 

areal biogeochemical and geochemical variability. Elementconcentration baselines for plant species and soils were then 

estimated for TRNP. Extensive sampling was not necessary 

to establish the baselines because the concentrations of most 

elements in the materials sampled at random locations were 

fairly uniform. The data should be useful in future studies 

when the chemistry of new samples, collected, prepared, 

and analyzed in the same manner as in this study, are 

compared with the baseline values. Further, a comparison 

of total-element concentration levels in the materials sampled with published values of toxicity thresholds for trace 

elements and sulfur indicates no current instances of phytotoxic or zootoxic conditions in the park. 

Of the elements determined in three plant species and 

soils collected downwind of a natural-gas processing facility near TRNP, only sulfur in tree lichen, boron in clubmoss, and sulfur in soil showed important inverse relations 

between concentration and increasing distance from the 

facility. Emissions from this facility were found to affect 

sulfur and boron levels up to about 4 km from the source. 

Everglades and Biscayne National Parks.-The 

study was designed to measure the relative importance of 

sulfur and trace-element emissions, from the oil-fired Turkey Point electrical power generation facility in south Dade 

County, Fla., on nearby vegetation. The purpose was to 

distinguish between anthropogenic and natural sulfur and 

trace-metal sources and to estimate the zone of measurable 

influence of the powerplant emissions (Gough, Jackson, 

and others, 1985). The zone of measurable influence of the 

powerplant could not be precisely defined by utilizing 

principally plant material collected along four traverses in 

the study area. This geographic region has an extremely 

complex set of ecosystems, and even though the operation 

of the powerplant has had some effect on the sulfur 

chemistry of nearby materials, a major regional influence 

could not be demonstrated. Levels of AI, Co, Cr, Cu, Ni, 

V, and Zn in vegetation do not markedly decrease with 

Cooperative Studies by the U.S. Geological Survey and the U.S. National Park Service in Environmental Biogeochemistry 53 
Figure 13.1. Past and present national park and recreation units investigated under the U.S. Geological 

Survey and National Park Service Cooperative Environmental Biogeochemistry project. 

increasing distance from the powerplant. The trace-metal 

data suggest, however, a shadow effect within 1 km of the 

emission stacks. 

Of the metal concentrations measured, only lead and 

sodium levels in plant materials might be considered large 

but not unusually so. Our results show a measurable marine 

influence, which helps explain the values for sodium. These 

values are fairly typical for coastal regions. Lead, on the 

other hand, is such a ubiquitous anthropogenic metal that 

multiple industrial sources are undoubtedly involved in its 

biotic concentration and distribution. 

The relative abundance of stable sulfur isotopes in 

vegetation helped discriminate the sulfur in vegetation that 

is being contributed by the sea from that which is being 

contributed by the operations of the powerplant. Samples of 

fuel oil from the powerplant possessed 834S values equal to 

about zero per mil, and the only similar 834S values in 

vegetation were found at a site about 1 km from the 

powerplant. Marine sulfate has a 834S value of about + 20 

per mil. Larger positive 834S values of samples collected 

elsewhere near the coast apparently reflect the addition of 

marine sulfate. 

Redwood National Park. -Redwood National Park 

(RNP) in northern California is close to vast lateritic nickel 

deposits. The proposed mining and milling activities at 

Gasquet Mountain will become a source of S02 and 

airborne metals. This source is expected to emit several 

hundred tons of so2 per year and an unknown, but 

potentially significant, quantity of trace metals, specifically 

Cr, Ni, Co, Fe, and Mn, which are all of environmental and 

biological importance. These emissions may have a direct 

local influence on the flora of the region. Tree lichens are 

known to concentrate metals and are also sensitive to 

elevated S02 levels. By measuring the background level of 

sulfur and metals in common lichen species before development of the resource, it will be possible to assess the 

potential for harmful so2 impacts and to monitor any 

increase in the trace-metal burdens in lichen tissue. This 

latter parameter would help signal the need for more 

detailed element cycling studies. 

SPECULATIONS AND RECOMMENDATIONS 

With the continued development of lands near 

national parks, preserves, and recreation areas, there is both 

a legal and an ecological interest in the definition of the 

impact of suspected point sources of airborne contaminants. 

In accordance with the Clean Air Act, the NPS must 

monitor potentially toxic trace elements and sulfur so that 

an unacceptable deterioration of pristine air does not occur. 

The introduction of increased levels of sulfur into park 

regions not only will affect the growth and reproduction of 

susceptible plant species but also will upset sensitive food 

54 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
chains. Further, an increase in the acidity of lakes or soils 

may increase the mobility of heavy metals, potentially 

causing localized phytotoxic conditions. The NPS and the 

USGS have continued to express an interest in supporting 

studies that define baseline geochemical and biogeochemical studies in park regions that they have identified as likely 

to undergo continued or future elemental impact. The 

USGS occupies an enviable position for providing necessary data for decisionmaking because it is viewed as an 

impartial third party with a strong earth science and associated analytical chemistry reputation. 

REFERENCES CITED 

Gough, L.P., Jackson, L.L., Severson, R.C., and Bennett, J.P., 

1985, Sources of sulfur and trace metals near Everglades 

park and adjacent agricultural lands of southern Florida, 

U.S.A. [in English], in Kabata-Pendias, Alina, ed., 

National Conference on Effects of Trace Pollutants on 

Agricultural Environmental Quality, 3d, May 28-30, 1985, 

Pulawy, Poland, Proceedings, v. 1 [in Polish]: Pulawy, 

Poland, Polish Institute of Soil Science and Plant Cultivation, p. 85-89. 

Gough, L.P., Peard, J.L., Severson, R.C., Jackson, L.L., Arbogast, B.F., Motooka, J.M., Snow, S.W., Engleman, E.E., 

and Bennett, J.P., 1985, Baseline elemental-composition 

of selected plants and soils, and assessment of airborne 

element contamination, Theodore Roosevelt National Park, 

North Dakota: U.S. Geological Survey Open-File Report 

85-251' 50 p. 

Jackson, L.L., Engleman, E.E., and Peard, J.L., 1985, Determination of total sulfur in lichens and plants by combustioninfrared analysis: Environmental Science and Technology, 

v. 19, p. 437-441. 

Cooperative Studies by the U.S. Geological Survey and the U.S. National Park Service in Environmental Biogeochemistry 55 

14. Monitoring Geochemical Processes 

with Geophysics 

By Gary R. Olhoeft 

The movement of electrical charge in a variety of 

physical and chemical processes may be observed directly 

by electrical geophysical methods. The chemical processes 

include oxidation-reduction reactions at the surfaces of 

metallic minerals in contact with water, ion exchange with 

the surfaces of clays and zeolites, and a variety of clayorganic reactions. 

By stimulating the Earth with an electrical current at 

varying frequencies and amplitudes and measuring the 

voltage response, these geochemical processes may be 

monitored by using the geophysical technique called complex resistivity. At a single frequency of measurement, the 

ratio of voltage to current multiplied by a geometric factor 

is the resistivity. The resistivity is a complex number having 

both magnitude and phase and may be nonlinear (Olhoeft, 

1979a,b). In the absence of chemical processes and at 

measurement frequencies below 1,000 Hz, the phase angle 

and nonlinear parameters of the complex resistivity are all 

very small numbers (ideally zero). As chemical processes 

become active, the phase and nonlinearities increase. 

The spectral shape of phase and nonlinearity versus 

frequency produces diagnostic indicators of the type of 

chemical process: barren, redox, ion exchange, or clay 

organic. Examples of these complex resistivity signatures 

have recently been reviewed by Olhoeft (1985). These 

measurements may be made in the laboratory (Olhoeft, 

1979a,b, 1985), in the borehole (Olhoeft and Scott, 1980), 

or from the surface of the Earth (Sumner, 1976; Olhoeft, 

1984). By varying the geometry of the electrode array, the 

volume of investigation may be altered to produce a 

three-dimensional picture of the geochemical activity. 

In Henderson, Nev., the separation of inorganic from 

organic components in a plume leaking from an industrial 

site was measured by complex resistivity. The inorganic 

component of the plume lowered the resistivity. The 

organic component of the plume depressed the normal 

phase response of the clays present at the site. The complex 

resistivity data showed that the inorganic components were 

contained above a clay aquitard, whereas the organic 

components had penetrated into the clay aquitard. Wenner 

array surface soundings, borehole electrical logs, and laboratory measurements on core samples having complex 

resistivity all agreed remarkably well (Olhoeft, 1984). 

In Willow Springs, La. , leakage from a landfill was 

measured by complex resistivity. Again, the inorganic 

portion of the plume was detected by a decrease in resistivity, and the organic portion was detected from a clayorganic reaction visible in the phase response. However, the 

character of the complex resistivity signature in Willow 

Springs was very different from that observed in Henderson. Figures 14.1 and 14.2 illustrate laboratory measurements on core samples from Henderson and Willow 

Springs, respectively. Note the phase differences between 

the contaminated and uncontaminated samples (for further 

details, see discussion of figures in Olhoeft, 1985). More 

laboratory work is required to identify the difference in the 

mechanisms between the two sites. 

The complex resistivity technique is slower and more 

expensive than the loop-loop electromagnetic induction 

technique. Loop-loop electromagnetic induction can map 

the location of resistivity anomalies caused by inorganic 

contaminants. Organic contaminants produce very small 

resistivity changes compared to the inorganic contaminants 

and are thus often masked by the presence of inorganic 

components. Only the complex resistivity technique can 

independently observe organic components reacting with 

clays. However, the complex resistivity technique cannot 

detect organic components that do not have clays. When 

clays are absent, ground-penetrating radar has a higher 

probability of detecting organic contaminants because of the 

contrast in dielectric permittivity between organic contaminants and soil-water systems. 

Monitoring Geochemical Processes with Geophysics 57 
2.5~------------------------------------------~ 

r 2.2 

E 

.c 

~ 1.9 ~ 

...... 

> 

...... 1.6 

U) 

U) 

Q) 

a: 1.3 

• 

1- . .._____ 

....... " "-

0.96 Percent RHO 

• 5.5 8 Percent RHO 

,.... . . 

'\ . '--·--·-·-·--·- . \ . .................... ·-·- . -~.....,..-.-.. . .........., ........................... ...._......._ ............... _.....__ 

1~-----~----------~-----------L----------~----------._ __________ ~-----~----------~----------~ 

...... 

-o 

tO 

L. 

E 

.......... 

Q) 

U) 

tO 

.c 

a.. 

I 

CJ 

g 

3 

2 

1 

~ o1 0.4 

UI Q;ra.. 

u.. -1 

CJ 

g 

C> 0.93 mrad PHD 

0 1.46 mrad PHD 

C> -Contaminated 3/1 0-1 2 

0 -Uncontaminated 5/2 0-2 2 

-3~----------+-----------~------4----------~----------4-----------~------4----------~-----~ 

-3 -2 -1 0 1 2 3 4 5 6 

LOG Frequency/Hz 

0 

C> 

Po =2.32, m= 0.647, F= 0.302, K00 =2250 

K00 Po =2.15, m= 0.759, F= 0.658, =31 40 

Figure 14.1. Complex resistivity spectra of montmorillonitic 

clay soil from Henderson, Nev., uncontaminated (circles) and 

contaminated (triangles) with organic waste from an industrial 

site. The shift in phase to lower frequency with contamination 

indicates inhibition of the cation exchange process by the 

organics. RHD, resistivity Hilbert distortion. PHD, phase 

Hilbert distortion. THD, total harmonic distortion. f, faradaic 

time constant distribution normalization factor. I f I faradiac 

time constant distribution remapped into the frequency 

domain. CJ'0 , DC resistivity in ohm-m. m, volume chargeability. 

Koo, high-frequency relative dielectric permittivity. See Olhoeft 

(1985, fig. 17) for a detailed explanation. 
9 

E 8 I 

E 

.c 

0 7 ' >-

+J 

> 

+J 6 

Cl) 

Cl) 

Q) 

a: 5 

4 

'"0 

ro 

'-

E 

' Q) 

Cl) 

ro 

.c 

a_ 

I 

(!) 

0 

_J 

3 

2 

1 

+J 

~ 0 3.5 

OI Q;.-

a_ 

lL -1 

(!) 

g 

0 

[> 

-2 

2.3 5 Percent RH D 

• 1.2 3 Percent RH D 

1> 0.77 mrad PHD 

0 

1> -Contaminated MW- 2 7 

0 -Uncontaminated MW- 2 2 

-1 0 1 2 3 4 5 

LOG Frequency/Hz 

Po =5.61, m= 0.586, F= 0.1 20, K00 =7 49 

Po =8.1 6, m= 0.669, F= 0.528, K00 =697 

6 

Figure 14.2. Complex resistivity spectra of clay soil from Willow 

Springs, La., uncontaminated (circles) and contaminated (triangles) with organic waste from a leaking landfill. In contrast to 

figure 14:1, the organic in this case probably is toluene, which 

interferes with charge movement between clay particles (Sadowski, 1988), in effect altering the way the clay particles "see" 

each other. See the caption of figure 14.1 for symbol definitions and Olhoeft (1985, 1986) for a detailed explanation. 

Monitoring Geochemical Processes with Geophysics 59 
REFERENCES CITED 

Olhoeft, G.R., 1979a, Electrical properties, in Hunt, G.R., and 

others, Initial report of the Petrophysics Laboratory: U.S. 

Geological Survey Circular 789, p. 1-25. 

---l979b, Nonlinear electrical properties, in Neel, L., ed., 

Nonlinear behavior of molecules, atoms and ions in electric, magnetic or electromagnetic fields: Amsterdam, 

Elsevier, p. 395-410. 

---1984, Clay-organic reactions measured with complex 

resistivity, in Expanded abstracts, 54th Annual International Meeting and Exposition of the Society of Exploration 

Geophysicists, Dec. 2-6, 1984, Atlanta, Ga.: Tulsa, Okla., 

Society of Exploration Geophysicists, p. 356-358. 

---1985, Low-frequency electrical properties: Geophysics, 

v. 50, no. 12, p. 2492-2503. 

---1986, Direct detection of hydrocarbon and organic chemicals with ground penetrating radar and complex resistivity, 

in Proceedings of the NWW AI API conference on Petroleum Hydrocarbons and Organic Chemicals in Ground 

Water-Prevention, detection, and restoration, Nov. 

12-14, 1986, Houston, Tex.: Dublin, Ohio, National 

Water Well Association, p. 285-305. 

Olhoeft, G.R., and Scott, J.H., 1980, Nonlinear complex resistivity logging, in Transactions of the 21st Annual SPWLA 

Logging Symposium: Houston, Tex., Society of Professional Well Logging Analysts, Inc., p. T1-T18. 

Sadowski, R.M., 1988, Clay-organic interactions: Golden, Colo., 

Colorado School of Mines, unpublished Master's thesis, 

209 p. 

Sumner, J.S., 1976, Principles of induced polarization for geophysical exploration: Amsterdam, Elsevier Scientific, 

277 p. 

60 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
15. Bedrock Geochemistry and the Environment 

By Jon J. Connor 

Bedrock geochemistry for the most part only indirectly influences the quality of the human environment, 

largely because a complex surficial cover (soils, plants) 

prevents much direct human contact with rocks (fig. 15.1). 

Even so, sedimentary rocks, which constitute perhaps 75 

percent of the near-surface bedrock in the conterminous 48 

States, do play an important role in two specific areas of 

environmental interest; they may control the chemistry of 

potable water supplies, and if exposed at the surface in large 

amounts (by mining, for example), they may drastically alter 

the surficial geochemical environment. 

The impact of reservoir rock on ground water, largely 

through pH control of metal content, can be of prime 

importance. Naturally soft water (low pH) tends to be 

higher in many trace metals than hard water (high pH), and 

much attention has been given to the possible role of hard 

and soft water in the etiology of heart disease in this country 

(Schroeder, 1960). The surficial effects of coal mining or 

metal ore extraction may easily result in the introduction of 

high concentrations of metals into the surface environment. 

As an example, chronic molybdenosis in cattle on a ranch in 

Ground water 

7 

Rocks 

GEOCHEMICAL PATHWAYS 

Figure 15.1. The role of rocks in influencing 

the near-surface geochemical environment. 

central Missouri was apparently induced by weathering of 

(and consequent metal transport from) a clay-pit spoil pile 

upstream of the ranch (Ebens and others, 1973). 

A knowledge of elemental abundances in sedimentary 

rocks is, therefore, important to geochemical studies of the 

surficial environment. However, little more has really been 

learned about trace-element concentrations in such rocks 

since the work of Turekian and Wedepohl (1961). Their 

summary of element abundance in sandstone, shale, and 

carbonate rock is widely accepted as the standard against 

which geochemical change or anomaly in the surficial 

environment is measured. The relatively narrow base on 

which their estimates were made and the wide compositional variation within the three classes of sedimentary rock, 

however, should give one pause if these estimates are used 

to evaluate local geochemical anomalies in the surface 

environment. 

Of the sedimentary rocks, shale is richest in most 

trace elements; estimates of expected metal content in shale 

are given in table 15.1. The first row lists the estimates of 

Turekian and Wedepohl. The second row gives estimates 

for a well-known organic-rich shale of Late Devonian to 

Early Mississippian age in Kentucky; such shales are known 

to be geochemically anomalous when compared to ordinary 

shales, but they may nonetheless constitute the norm in 

local areas. The third row lists estimates for a weakly 

metamorphosed (greenschist facies) shale of Middle Proterozoic age in western Montana, and the last row gives 

estimates for shale of Late Proterozoic? to Early Cambrian? 

age in the Western United States. 

Consistency among the estimates ranges from good to 

bad. For example, the estimates in barium range from 510 

to 620 parts per million (ppm) and for cobalt from 8 to 19 

ppm, but ranges among the other elements are much 

broader. Molybdenum in black shale is high by a factor of 

about 25 compared with expected values of molybdenum in 

the other units, and manganese in black shale is low by a 

factor of about 6 or more. A wide disparity is seen in lead 

and copper, even if the copper-rich black shale is excluded. 

Incidentally, the shale having an expected concentration of 

5 ppm copper is a "copper-shale"; that is, the unit contains 

copper deposits. 

Bedrock Geochemistry and the Environment 61 
Table 15.1. Estimates of expected metal concentration in shale 

Unit1 Element (in parts per million) 

Barium Cobalt Molybdenum Manganese Lead Copper 

1 ....................... 580 19 2.6 850 20 45 

2 ....................... 510 8.1 72 65 23 130 

3 ....................... 620 12 <2 380 10 5 

4 ....................... 510 13 <4 420 <3 14 

1 Unit 1-Shale, unrestricted (Turekian and Wedepohl, 1961); Unit 2-Chattanooga, Ohio, and New 

Albany Shales in Kentucky (Connor and Shacklette. 1975); Unit 3-Spokane, Grinnell, and St. Regis 

Formations in northwest Montana (J.J. Connor, unpub. data); Unit 4-Sauk sequence in Western United 

States (Connor and Shacklette, 197 5). 

The point of these comparisons is not to argue that 

some estimates are better than others, but rather to argue 

that wide (and legitimate) differences exist in estimates of 

expected concentration in lithically similar bedrock. 

Turekian and Wedepohl' s estimates are of worldwide 

(crustal) application and are subject to unknown error, to 

which these authors freely admit. The remaining estimates, 

each representing a coherent stratigraphic unit within a 

known geologic setting, pertain to well-defined units of 

lesser, but still regionaL extent. Estimates in these smaller 

units (rows 2, 3, and 4, in table 15.1) are clearly superior 

for evaluating anomalous surficial geochemistry in their 

respective areas of subcrop, but they are more costly to 

produce. The wide scatter in the estimates illuminates the 

magnitude of effort in field and laboratory work, which is 

needed if serious evaluation of the geologic substrate as a 

trace-element source to the surface environment is to be 

continued. 

REFERENCES CITED 

Connor, J.J., and Shacklette, H.T., 1975, Background geochemistry of some rocks, soils, plants, and vegetables in the 

conterminous United States: U.S. Geological Survey Professional Paper 574-F, 168 p. 

Ebens, R.J., Erdman, J.A., Feder, G.L., Case, A.A., and Selby, 

L.A., 1973, Geochemical anomalies of a claypit area, 

Callaway County, Missouri, and related metabolic imbalance in beef cattle: U.S. Geological Survey Professional 

Paper 807, 24 p. 

Schroeder, H.A., 1960, Relation between hardness of water and 

death rates from certain chronic and degenerative diseases 

in the United States: Journal of Chronic Diseases, v. 12, 

p. 586. 

Turekian, K.K., and Wedepohl, K.H., 1961, Distribution of 

elements in some major units ofthe Earth's crust: Geological Society of America Bulletin, v. 72, no. 12, 

p. 175-191. 

62 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
16. Geochemistry of Rock-Water Reactions in 

Basalt Aquifers of the Columbia River Plateau 

By Paul P. Hearn, Jr., William C. Steinkampf, Lloyd D. White, and John R. Evans 

INTRODUCTION 

Understanding the interactions between ground water 

and aquifer materials is critical to any study involving the 

geochemistry of ground water; knowledge of mineral-water 

reactions can provide valuable information regarding the 

chemical evolution of ground water and often may give 

important insights into other hydrological processes. This 

report summarizes the results of a geochemical and oxygenisotope study of the basalt aquifers of the Columbia River 

Plateau. A conceptual model for the chemical evolution of 

Columbia River Plateau ground water is described on the 

basis of the composition and paragenesis of secondary 

phases and progressive changes in ground-water chemistry 

with increasing residence time in the system. Oxygenisotope data are used to estimate the formation temperatures 

of secondary minerals and to place initial constraints on the 

timing of alteration reactions. 

COLUMBIA RIVER PLATEAU 

The Columbia River Plateau is a structural and 

topographic basin and has its lowest point near Pasco, 

Wash. The rocks of the plateau are primarily flat-lying 

flood basalts of Miocene age, which reach thicknesses of 

more than 1,500 m in the central part of the basin. The 

hydrologic system considered here is bounded on the north 

by the Columbia River, on the east by the WashingtonIdaho border, on the south by the Blue Mountains, and on 

the west by a line midway between the Columbia River and 

the Cascade Range. The vertical and areal extents of the 

major aquifers were mapped by Drost and Whiteman ( 1986) 

on the basis of records from some 2,500 water wells within 

this area. Hearn, Steinkampf, Bortleson, and Drost (1985) 

described regional trends in ground-water chemistry and 

secondary alteration on the basis of ground-water data from 

49 of these wells and on analyses of secondary alteration 

obtained from outcrops, drill cuttings, and core samples 

from the Hanford test site (fig. 16.1). 

MINERALOGY AND PARAGENESIS OF 

SECONDARY ALTERATION 

Secondary minerals in the Columbia River basalt tend 

to be concentrated in the fractured and vesicular zones in the 

bases and tops of individual basalt flows; these zones 

generally represent the major pathways of ground-water 

flow. Studies by Ames (1980), Benson and Teague (1982), 

and Hearn, Steinkampf, Bortleson, and Drost (1985) have 

shown that the most common secondary minerals include a 

smectite close to nontronite in composition, the zeolite 

clinoptilolite, iron oxide of indeterminate crystallinity, 

opaline silica, and quartz. Although other secondary phases 

are common, they occur mostly in minor or trace amounts. 

On the basis of the sequence of alteration observed in 

vesicles and fractures, and vertical differences in the relative amounts of secondary phases, Benson and Teague 

( 1982) proposed the following paragenetic sequence: clay 

(mostly nontronite)~linoptilolite~silica and (or) clay. 

Hearn, Steinkamp, Bortleson, and Drost (1985) also found 

appreciable iron oxide intergrown with early smectite in 

samples above 1,000 feet. 

Secondary alteration of the basalt appears to occur 

almost exclusively at low ( < 100 °C) temperatures by 

reaction with ground water. There is no evidence of any 

hydrothermal alteration. This conclusion is supported by the 

mineralogy of the alteration assemblage (Benson and 

Teague, 1982; Hearn, Steinkampf, Bortleson, and Drost, 

1985) and by oxygen-isotope data (Hearn, Steinkampf, 

Bums, and others, 1985). 

Volcanic glass is by far the most unstable phase in 

fresh basalt, due to its lack of crystal structure and extensive 

surface area (Jones, 1966), and for this reason is probably 

the major solid phase participating in reactions with ground 

water. By comparing analyses of fresh glass with analyses 

of early smectite and clinoptilolite, one can get a general 

idea of alteration reaction pathways (table 16.1). Early 

smectite is significantly enriched in iron and magnesium 

and depleted in sodium, potassium, and calcium relative to 

volcanic glass. The marked enrichment of smectite in 

magnesium probably reflects the contribution of this element from the dissolution of pyroxene. In the later clinopGeochemistry of Rock-Water Reactions in Basalt Aquifers of the Columbia River Plateau 63 
0 

121 

0 

0 0 

0 

0 

0 0 0 

~ 0 

oo 

00. 

oo 

0 

0 

118 

eo 

• 

0 

0 

0 

0 

0 

0 117 

47° 

0 

I 

0 

20 40 MILES 

I I I I I I 

20 40 60 KILOMETERS 

EXPLANATION 

e Sampling sife for secondary minerals 

o Water well 

Figure 16.1. Study area in the Columbia River Plateau showing location of water wells and sampling sites for 

secondary minerals. 

Table 16.1. Compositional variation during paragenesis 

[Elements in weight percent; data normalized on a water-free basis, analysis by electron probe and SEM/EDS] 

Silica Iron Sodium Potassium Calcium Magnesium No. of 

samples 

Entablature glass 1 •••••••••.•.. 30.0 6.1 3.5 2.2 2.6 0.3 60 

Smectite2 .........•••......... 29.2 9.8 1.1 .7 1.2 5.6 40 

Clinoptilolite2 ••••••••••••••••• 34.0 .4 4.2 2.2 1.1 .2 30 

1 Long and Strope, 1983. 2 Hearn, Steinkampf, Bartleson, and Drost, 1985. 

64 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Na EXPLANATION 

Carbon-14, in percent 

modern carbon 

Older 

o Less than 35 

t • 35 - 65 

00 than 65 

co 0 Younger 

eo 

6* • A • 

0 <o. 

0 

• • ' A o&> 

• A 0-

A ·~ oe A I 

.. 

' A 

AA -

oe 

Ca~------------------------------~------------------------------~Mg 

Figure 16.2. Molar plot of dissolved sodium, calcium, and magnesium concentrations in ground 

water, grouped in terms of relative age, Columbia River Plateau. 

tilolite, the early trend is dramatically reversed; relative to 

the early smectites, the clinoptilolites are enriched in silica, 

sodium, and potassium and depleted in iron and magnesium. 

CHEMICAL EVOLUTION OF GROUND WATER 

Alteration reactions are also reflected by progressive 

changes in ground-water chemistry with increasing residence time in the system. A cation plot of dissolved 

sodium, magnesium, and calcium grouped in terms of 

relative ground water age shows a progressive enrichment 

of sodium with increasing age and a concurrent depletion of 

calcium and magnesium; the Ca:Mg remains fairly constant 

(fig. 16.2). Progressive trends are also apparent in several 

other constituents (fig. 16.3). Dissolved silica, potassium, 

and pH all increase with increasing residence time, whereas 

dissolved oxygen becomes progressively depleted. No corresponding trends are visible in the anion suite; bicarbonate 

is the predominant species in most samples (Hearn, 

Steinkampf, Bartleson, and Drost, 1985). 

CONCEPTUAL MODEL OF ROCK-WATER 

REACTIONS 

On the basis of the paragenetic sequence of secondary 

alteration and the progressive changes in water chemistry 

with increasing residence time, it is possible to construct a 

conceptual model describing the chemical evolution of 

ground water in the system. This model is similar in 

principle to the one proposed by Jones (1966). The primary 

reactants in the basalt are volcanic glass and pyroxene; 

plagioclase feldspar and iron-titanium oxides are thermochemically more stable and contribute substantially less 

material to solution (Jones, 1966; Benson and Teague, 

1982). Dissolution proceeds primarily through hydrolysis; 

although C02 may participate in this process close to the 

ground surface, the generally thin soil cover suggests that 

its role is minor. The first solid products of this process are 

smectite and in some cases amorphous iron. Some evidence 

suggests that smectite may form by the gradual ordering of 

metastable amorphous compounds of silicon, aluminum, 

and other cations (Paces, 1978). As the hydrolysis reactions 

Geochemistry of Rock-Water Reactions in Basalt Aquifers of the Columbia River Plateau 65 
n=12 n=17 n=20 

70~----------------------------------~ 

60 

50 

Sl 

(ppm)40 

30 

10 

8 K 

(ppm) 6 

4 

8 pH 

7 

8 

DO 6 

(mg/U 4 

2 

65-100 

younger 

65-35 

%Modern 14C 

0-35 

older 

Figure 16.3. Average concentrations of dissolved silicon 

and potassium, dissolved oxygen (DO), and pH, plotted in 

terms of relative ground-water age, Columbia River Plateau. ppm, parts per million; n, number of samples. 

proceed, the continued release of hydroxyl drives the pH 

upward and eventually precipitates calcite. Dissolved oxygen is consumed by the oxidation of ferrous iron in volcanic 

glass and pyroxene. In the early stages of alteration, silica, 

sodium, and potassium are all contributed to solution more 

rapidly than they are removed by precipitation, and the 

concentrations of these cations steadily increase. This 

process eventually produces alkaline ground waters supersaturated with clinoptilolite and silica, and these phases 

begin to precipitate. 

OXYGEN ISOTOPE GEOTHERMOMETRY 

Whereas abundant geologic and mineralogic evidence 

suggests that secondary alteration in the Columbia River 

basalt is a low-temperature phenomenon, the most convincing support for this contention is provided by oxygenisotope geothermometry of secondary minerals. 

Samples of vug-filling smectite, calcite, and silica 

were hand picked from surface outcrops, water-well drill 

chips, and drill core from test wells at the Hanford test site 

(fig. 16.1). All samples were screened by X-ray diffraction 

(XRD) and scanning electron microscopy/energy-dispersive 

X-ray fluorescence spectroscopy (SEM/EDS) to ensure 

their purity, prior to isotopic analysis. Oxygen isotope data 

for ground water from within the test site were obtained 

from Early and others (1985). 

Formation temperatures of secondary minerals were 

computed by using mineral-water geothermometric equations of Y eh and Savin ( 1977) for smectite, Clayton and 

others (1972) for silica, and O'Neil and others (1969) for 

calcite. Formation temperatures for each sample were 

computed by using the closest available ground water 8180 

values. The results of these computations are plotted as a 

function of depth in figure 16.4. The computed formation 

temperatures for smectite, calcite, and silica all increase 

with depth. A least-squares fit of the data yields a gradient 

of approximately 46 °C, close to the thermal gradient of 

approximately 40 °C/km observed at the test site today. The 

difference is largely a reflection of the data from points 

shallower than 600 m; formation temperatures for these 

samples fall consistently below the local thermal gradient, 

whereas formation temperatures for deeper samples are 

evenly clustered around the thermal gradient. This discrepancy, together with the large amount of scatter in these data, 

most likely is due to the fact that the secondary minerals 

precipitated from ground water having a different oxygenisotope composition than present-day ground waters. These 

differences may be both random (due to small-scale flow 

heterogeneities) and systematic (due to unidirectional or 

secular changes). 

These preliminary results support the contention that 

secondary alteration of the basalts is a low-temperature, as 

opposed to a hydrothermal, process. Furthermore, the 

congruity of the formation temperatures with the presentday thermal gradient suggests that the alteration assemblage 

formed after the emplacement of the greater part of the 

basalt sequence. This contention is consistent with the ages 

of the constituent basalt flows and with estimated rates of 

alteration in deep-sea basalts. Studies of midocean-ridge 

basalts (MORB) indicate that low-temperature alteration by 

seawater begins immediately after cooling; however, significant perturbation of MORB 8180 values from primary 

magmatic values appears to require a minimum of 1 to 2 

million years (Muehlenbachs, 1986). The Grande Ronde 

and Wanapum Basalts, which constitute over 90 percent of 

the vertical thickness of basalt at the test site, were 

emplaced within an interval of approximately 2 million 

years (14.5 to 16.5 Ma). Although seawater alteration data 

obviously cannot be applied directly to a freshwater system, 

these observations agree well with the contention that 

secondary minerals did not equilibrate isotopically with 

ground waters until the greater part of the basalt flows had 

cooled to ambient temperatures. 

66 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
-

u 

0 

-(JJ 

Q:: 

:J 

~ 

<C 

Q:: 

(JJ 

~ 

~ (JJ 

~ 

100 

90 

80 

70 

60 

50 

40 

30 

20 

10 

0 

-10 

Explanation 

• Smectite 

a Calcite 

+ Silica 

Least squares fit 

Geothermal 

gradient 

0 200 400 600 800 1000 1200 1400 1600 

DEPTH (METERS) 

Figure 16.4. Formation temperatures computed by using in-situ 8

180 values. 

CONCLUSIONS 

The chemical evolution of ground water in basalt 

aquifers of the Columbia River Plateau is determined 

primarily by the hydrolysis of volcanic glass and pyroxene 

and the stoichiometry of secondary alteration products. This 

conclusion is supported by progressive changes in solute 

chemistry with increasing residence time and the composition and sequence of formation of secondary minerals. 

Ground water progressively evolves from a calciummagnesium bicarbonate type in shallow upgradient sites to 

a sodium-potassium bicarbonate type in deeper downgradient sites. 

Formation temperatures computed from oxygenisotope analyses of secondary minerals indicate that alteration took place at temperatures roughly concordant with 

the present-day geothermal gradient of 40 °C/km. This 

relation suggests that secondary minerals did not equilibrate 

isotopically with surrounding ground water until the greater 

part of the total thickness of basalt (Grande Ronde and 

Wanapum Basalts) had cooled to ambient temperatures. 

REFERENCES 

Allen, C.C., and Strope, M.B., 1983, Microcharacterization of 

basalt-Considerations for a nuclear waste repository, in 

Gooley, R., ed., Microbeam analysis: San Francisco, 

Calif., San Francisco Press, p. 51-53. 

Ames, L.L., 1980, Hanford basalt flow mineralogy: Battelle 

Institute Pacific Northwest Laboratory, Report no. 

PNL-2847, 447 p. 

Benson, L.V., and Teague, L.S., 1982, Diagenesis of basalts 

from the Pasco Basin, Washington, I, Distribution and 

composition of secondary mineral phases: Journal of Sedimentary Petrology, v. 52, no. 2, p. 595--613. 

Clayton, R.N., Rex, W.R., Syers, J.K., and Jackson, M.L., 

1972, Oxygen isotope abundance in quartz from Pacific 

pelagic sediments: Journal of Geophysical Research, v. 77, 

p. 3057-3067. 

Drost, B.W., and Whiteman, K.J., 1986, Surficial geology, 

structure, and thickness of selected geohydrologic units in 

the Columbia Plateau, Washington: U.S. Geological Survey Water-Resources Investigations Report 84--4326, scale 

1:500,000. 

Early, T.O., Mudd, R.D., Spice, G.D., and Starr. D.L., 1985, A 

hydrochemical data base for the Hanford Site: Rockwell 

Hanford Operations Report BWI-DP--061, 347 p. 

Hearn, P.P., Steinkampf, W.C., Bortleson, G.C., and Drost, 

B. W., 1985, Geochemical controls on dissolved sodium in 

basalt aquifers of the Columbia Plateau, Washington: U.S. 

Geological Survey Water-Resources Investigations Report 

84-4304, 38 p. 

Hearn, P.P., Steinkampf, W.C., Bums, M.G., White, Doug, and 

Brown, Z.A., 1985, Oxygen isotope geothermometry of 

secondary minerals in the Columbia River Basalt, Washington State [abs.]: Eos (Transactions, American Geophysical Union), v. 66, no. 46, p. 909. 

Geochemistry of Rock-Water Reactions in Basalt Aquifers of the Columbia River Plateau 67 
Jones, B.F., 1966, Geochemical evolution of closed basin water in 

the western Great Basin, in Rau. J .L., ed., Second symposium on salt, v. 1, Geology, geochemistry, mining: 

Cleveland, Ohio. Northern Ohio Geological Society, 

p. 181-200. 

Long, P.E., and Strope, M.B., 1983, Composition of augite and 

pigeonite in basalt flows that are candidates for a nuclear 

waste repository, in Gooley, R., ed., Micro beam analysis: 

San Francisco, Calif., San Francisco Press, p. 57-60. 

Muehlenbachs, K., 1986, Alteration of the oceanic crust and the 180 history of seawater, in Valley, J. W. , Taylor, H. P. , and 

O'Neil. J .R., eds., Stable isotopes in high temperature 

geological processes: Reviews in Mineralogy, v. 16, 

p. 425-444. 

O'Neil, J.R., Clayton, R.N., and Mayeda, T.K., 1969, Oxygen 

isotope fractionation in divalent metal carbonates: Journal 

of Chemical Physics, v. 51, no. 2, p. 5547-5558. 

Paces, Tomas, 1978, Reversible control of aqueous aluminum and 

silica during the irreversible evolution of natural waters: 

Geochimica et Cosmochimica Acta, v. 42, no. 10, 

p. 1487-1494. 

Swanson, D.A., 1967, Yakima Basalt of the Tieton River area, 

south-central Washington: Geological Society of America 

Bulletin, v. 78, no. 9, p. 1077-1109. 

Yeh, H.W., and Savin, S.M., 1977, Mechanism of burial metamorphism of argillaceous sediments, pt. 3, 0-isotope 

evidence: Geological Society of America Bulletin, v. 88, 

p. 1321-1330. 

68 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
17. Early Diagenesis and Metal-Organic Matter 

Interactions in Alkaline Playa Lakes of the 

Lahontan Basin, Nevada 

ByW.H. Orem 

Playa or alkaline lakes form in basins or depressions 

isolated from the sea where evaporation exceeds freshwater 

input. The dissolved solids in the freshwater entering the 

lake are concentrated by evaporation, ultimately forming 

hypersaline and (or) alkaline conditions in the lake. Playa 

lakes have great economic importance as sources of minerals and metal ores and in some cases as areas of oil and gas 

formation. Also, studies of the geochemistry of natural 

playas may provide useful insight into toxic metal problems 

associated with reservoirs and irrigation in arid and semiarid 

regions. Despite this, playa lakes and evaporitic environments in general remain one of the most poorly unilerstood 

biogeochemical systems on Earth. 

This paper presents some very preliminary geochemical data on sediments and pore water from Carson Lake, 

Nev. The long-range objective of this project is to establish 

the processes involved in the early diagenesis of organic 

matter in playa lakes and the extent and significance of 

metal-organic matter interactions in these systems. 

Carson Lake is a shallow playa (water depth of about 

30 em in August 1985) located near Fallon, Nev. This lake 

represents the terminus of the Carson River, which flows 

eastward from the Sierra Nevada Mountains. The lake is 

surrounded by a salt marsh and had a pH of about 9. 5 at the 

time of sampling. Titration of the overlying and pore waters 

with 0.1 M HCl gave a titration curve having an inflection 

point at a pH of about 4.5. This curve is indicative of 

alkalinity in the lake dominated by bicarbonate and carbonate ions. 

The sediment of the lake is composed of an organicrich upper layer (2 em depth) and a sticky clay below. The 

organic carbon data from an auger sample taken in the lake 

show a steady decrease in percent organic carbon with 

increasing depth (table 17 .1). This decrease may indicate 

that the salt marsh surrounding the lake is a relatively recent 

feature or that organic matter deposited in the sediments is 

readily degraded or solubilized under the highly alkaline 

conditions present in the lake. Dissolved organic carbon 

concentrations in the pore waters are relatively high (about 

100 mg/L of carbon). Thus, significant degradation (probably via sulfate reduction) and solubilization of the sedimentary organic matter are taking place. 

One major goal of this preliminary study was to 

determine the gross chemical structure of the dissolved 

organic matter (DOM) in the pore water to evaluate its 

metal binding characteristics. This isolation of the DOM 

was accomplished by using ultrafiltration; its chemical 

structure, determined by using elemental analysis and 13C 

nuclear magnetic resonance (NMR) spectroscopy, is dominated by a peak at 175 parts per million (ppm); this peak is 

indicative of carboxyl and (or) amide carbons (fig. 17 .1). 

The low nitrogen content (2.4 percent) and high oxygen 

content (62.4 percent) of the DOM, however, suggests that 

this peak must be predominantly due to carboxyl carbons. 

This finding, coupled with the unusually high atomic O:C 

of about 1.4 for this material, suggests that the DOM is 

composed primarily of multicarboxylic acids. This situation 

may be unique to alkaline lakes, because similar structures 

in the DOM have not been observed from a number of other 

sedimentary environments. This finding is significant, as 

di- and tricarboxylic acids are excellent binders of trace 

metals. I am pursuing this aspect of the overall study to 

obtain more detailed structural information. 

Some preliminary data on the major- and minorelement composition of Carson Lake sediments are shown 

in table 17 .2. The data suggest that little or no precipitation 

of typical evaporitic minerals is taking place in Carson 

Lake. The sediments appear to be composed of predominantly aluminosilicate clays that are probably highly altered 

Table 17.1. Organic-matter composition of Carson Lake 

sediments 

Depth 

(d) 

0-30 ........................ . 

30-60 ........................ . 

60-90 ........................ . 

90-120 ........................ . 

120-150 ........................ . 

Carbon 

(percent) 

2.6 

1.4 

1.6 

1.8 

1.0 

Nitrogen 

(percent) 

0.3 

.2 

1.0 

.3 

.9 

Early Diagenesis and Metal-Organic Matter Interactions in Alkaline Playa Lakes of the Lahontan Basin, Nevada 69 
Elemental Data 

%C %H %N %0 

31 .4 3.8 2.4 6 2.4 

(mineral matter-free basis) 

250 200 150 100 50 0 -50 -100 

Figure 17.1. Elemental data and 13C nuclear magnetic resonance spectrum of dissolved organic matter isolated from an 

alkaline playa lake, Carson Lake, Nev. ppm, parts per million. 

Table 17.2. Major- and minor-element composition of Carson Lake sediments 

[Measurements in percent, except as noted. ppm, parts per million] 

Depth Si AI Fe Ca 

(em) 

0-30 ...................... 47.4 16.1 17.6 6.7 

30-60 ...................... 50.5 17.3 17.8 4.7 

60-90 ...................... 59.3 17.1 17.0 4.6 

90-120 ...................... 47.7 17.2 18.1 5.2 

120-150 ...................... 51.8 18.8 15.5 4.8 

by reverse-weathering-type reactions. Iron concentrations 

are relatively high, possibly due to the formation of authigenic mineral phases. The copper, zinc, and lead concentrations are typical for modern lacustrine sediments but 

show an interesting decrease in concentration with increasing depth. This trend correlates with the decrease in organic 

matter content in the sediment with depth mentioned earlier. 

K Mg Na Ti Cu Zn Pb 

(ppm) (ppm) (ppm) 

5.6 3.6 1.6 0.8 69.44 100.21 20.58 

5.1 3.0 .7 .6 51.98 93.93 13.85 

5.1 4.6 1.5 .7 48.64 95.45 13.08 

4.9 3.6 2.4 .7 47.99 97.84 13.86 

4.8 3.3 .9 .0 39.96 90.16 10.44 

In summary, early diagenetic processes in sediments 

from Carson Lake are generating DOMin the pore waters 

having a very unusual chemical structure dominated by 

carboxyl groups. Such structures are ideal for binding metal 

ions, and alkaline lakes such as Carson Lake may be ideal 

environments for undertaking studies of interactions 

between metals and organic matter. 

70 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
18. The Role of Organic Matter in Weathering 

Processes 

By R. K. Kotra 

Of major importance to environmental geochemistry 

is an understanding of weathering processes and the types 

and rates of interaction among the many geochemical 

variables that influence weathering processes. The 

geochemistry of weathering has been extensively studied 

with emphasis primarily on the inorganic species. The role 

of organic matter during weathering has been studied in 

much less detail. 

Dissolved organic substances may play an important 

role in the breakdown of primary minerals in a variety of 

environments. The concentrations of organic solutes in 

surface waters and deeper waters can influence the pH and 

the redox potential. Organic solutes also can serve as 

complexing agents to mobilize some rna jor elements. The 

chief solutes appear to be organic acids. These can be low 

molecular weight acids such as the aliphatic mono- and 

dicarboxylic acids and the aromatic phenols or high molecular weight substances such as humic and fulvic acids. 

Carothers and Kharaka ( 1978) and Kharaka and 

others (1985) showed that oil-field waters from the Texas 

Gulf Coast and the San Joaquin Valley of California can 

contain as much as 5,000 parts per million (ppm) carboxylic 

acids in the temperature range 80-200 °C. Carboxylic acid 

anions contributed 50-100 percent of the measured alkalinity especially in the 80-120 °C range. At higher temperatures, carboxylic acids are gradually destroyed by decarboxylation reactions. The nature and concentration of 

phenolic species present in oil-field waters are poorly 

understood. Preliminary estimates indicate that phenolic 

compounds constitute 5-10 percent of dissolved organic 

carbon (DOC) of the brines from the southern San Joaquin 

Valley (Surdam and Crossey, 1985). 

The relation between organic acids and the preservation and (or) enhancement of porosity in sandstone and 

shale sequences in hydrocarbon reservoirs has been examined (Surdam and Crossey, 1985, and references therein). 

The organic acids are thought to be derived from thermal 

and catalytic decomposition of the kerogen (insoluble disseminated organic matter in sedimentary rocks) in the 

source rocks. An optimum diagenetic scenario for the 

preservation and (or) enhancement of porosity requires that 

organic-rich rocks be adjacent to potential reservoir rocks 

and requires a rapid evolution from organic-acid generation 

to hydrocarbon maturation. 

Antweiler and Drever (1983) reported that the weathering of an upper Tertiary volcanic ash in Wyoming was 

controlled by the presence of soluble organic acids derived 

from vegetation and soil. Both higher molecular weight 

dissolved organic matter (for example, humic and fulvic 

acids), as well as small organic anions (for example, 

formate, acetate, and oxalate), were present in the waters 

that influenced weathering. The concentrations of Na, K, 

Ca, Mg, AI, and Fe correlated with DOC and followed an 

annual cycle that had a maximum in the spring. 

Preliminary results from a study on the early diagenesis and metal-organic matter interactions in an alkaline 

playa lake indicate that the high-molecular-weight dissolved 

organic matter (DOM) has an unusual chemical structure 

(W.H. Orem, this volume). The material has a high atomic 

O:C and appears to be dominated by carboxyl functional 

groups. 

In the cases cited above, the source of the organic 

acids was vegetation, soil, and kerogen. Understanding the 

nature and origin of these source materials is important to 

predict the results of chemical alteration of mineral matter. 

For example, kerogen is the most abundant form of fixed 

organic matter in the crust of the Earth. The chemical 

structure of kerogen is complex and poorly understood 

despite many years of investigation. One classification 

scheme divides kerogen into three types on the basis of 

atomic H:C and O:C (Tissot and Welte, 1984). Type I 

kerogen is rich is aliphatic structures and is characterized by 

high hydrogen content such as that seen in some algal 

deposits. Type III kerogen is rich in polyaromatic structures 

and oxygen similar to plants of terrestrial origin. Type II 

kerogen is of intermediate composition. The chemical 

structure of humic substances is also complex. Application 

of new analytical approaches has recently resulted in much 

additional information concerning their origin and structure 

(for example, Christman and Gjessing, 1983). Recent 

studies on the high molecular weight DOM in pore waters 

from sediments have shown that the structure of the DOM 

The Role of Organic Matter in Weathering Processes 71 
is strongly influenced by the environment in which it is 

formed (Orem and Hatcher, 1987). 

An integrated approach to the study of the effects of 

organic matter on weathering requires characterization of 

dissolved organic species in waters, as well as of the parent 

organic matter. The nature and abundance of the parent 

organic matter may have a direct bearing on the type and 

quantity of organic acids that are active in a given setting. 

Furthermore, the role of organic bases has not been investigated. The organic solutes may exist for only short periods 

of time, but their influence on the composition of ground 

and surface waters is significant and in some cases may be 

the controlling factor. 

The role of organic matter in weathering processes is 

best examined by field studies in conjunction with laboratory simulations of the production of organic weathering 

agents under differing conditions and the effect of these 

agents on various mineral groups. Any assessments of the 

role of organic species in weathering will also have to 

consider the role of inorganic species; thus it is important to 

determine the forms of the major and trace elements in soils 

and waters. The results of such combined organic and 

inorganic geochemical investigations will be useful in 

understanding the interaction between organic matter and 

toxic inorganic elements, the transport of naturally occurring toxic materials, and their cause-and-effect relation to 

plant and soil microbe communities. 

REFERENCES CITED 

Antweiler, R. C. , and Drever, J. I. , 1983, The weathering of a late 

Tertiary volcanic ash; importance of organic solutes: 

Geochimica et Cosmochimica Acta, v. 47, no. 3, 

p. 623-629. 

Carothers, W.W., and Kharaka, Y.K., 1978, Aliphatic acid 

anions in oil-field waters; implications for origin of natural 

gas: American Association of Petroleum Geologists Bulletin, v. 62, no. 12, p. 2441-2453. 

Christman, R.F., and Gjessing, E.T., eds., 1983, Aquatic and 

terrestrial humic materials: Ann Arbor, Mich., Ann Arbor 

Science, 538 p. 

Kharaka, Y.K., Hull, R.W., and Carothers, W.W., 1985, Water/ 

rock interactions in sedimentary basins, chap. 2, in Relationship of organic matter and mineral diagenesis: Tulsa, 

Okla., Society of Economic Paleontologists and Mineralogists, SEPM Short Course 17, p. 79-176. 

Orem, W.H., and Hatcher, P.G., 1987, Solid-state 13C NMR 

studies of dissolved organic matter in pore waters from 

different depositional environments: Organic Geochemistry, v. 11, no. 2, p. 73-82. 

Surdam, R.C., and Crossey, L.J., 1985, Mechanisms of organic/ 

inorganic interactions in sandstone/shale sequences, 

chap. 3, in Relationship or organic matter and mineral 

diagenesis: Tulsa, Okla., Society of Economic Paleontologists and Mineralogists, SEPM Short Course 17, 

p. 177-232. 

Tissot, B.P., and Welte, D.H., 1984, Petroleum formation and 

occurrences (2d ed.): Berlin, Springer Verlag, 699 p. 

72 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
19. Application of Geophysical Methods to the 

Study of Pollution Associated with Abandoned 

and Injection Wells 

By Frank C. Frischknecht1 

INTRODUCTION 

Contamination of ground-water supplies by brine and 

other pollutants is a serious problem in some oil-producing 

and industrial areas. Abandoned petroleum and water wells 

and active injection wells are often major elements in the 

contamination process. The casings of abandoned wells 

develop leaks, and, if not properly plugged, such wells 

sometimes serve as conduits for pollutants to reach freshwater aquifers. Pollutants from waste-disposal sites or 

accidental spills may migrate down abandoned wells. 

Brines or other wastes injected into deep horizons may 

migrate up abandoned wells and reach aquifers containing 

potable water. Injection wells sometimes develop leaks and, 

if not carefully monitored, can pollute large volumes of 

earth materials before the effect is noted in production wells 

or at the surface. As a first step in the mitigation of these 

problems, methods of locating abandoned wells and mapping brine contamination from injection wells have been 

studied by the U.S. Geological Survey in cooperation with 

the U.S. Environmental Protection Agency (EPA). 

LOCATION OF ABANDONED WELLS 

Pollution caused by abandoned or unknown wells is 

especially acute in regions where there are old petroleum 

fields or extensive agricultural areas that have been irrigated 

from water wells. In 1979, there were estimated to be as 

many as 1,800,000 producing, dormant, and abandoned 

wells in the United States (Federal Register, 1979). In local 

areas, the number of wells is as high as 2,000 per square 

mile. In the early days of petroleum production, the 

locations of wells were not always recorded. Available 

records are sometimes inaccurate, and, in some States, 

locations were recorded only in terms of land subdivisions 

such as quarter sections. In some older agricultural areas, 

1 Deceased. 

systematic records of water wells were not kept. Therefore, 

there is a need for direct methods of locating abandoned 

wells. 

Magnetic and geoelectrical methods were evaluated 

for use in locating abandoned wells. A few geoelectrical 

methods were found to be useful in special applications, 

such as mapping the buried horizontal pipelines that are 

often associated with wells (Frischknecht and others, 1983; 

Jachens and others, 1986). However, the magnetic method 

proved to be much more useful for most purposes. 

In evaluation of the magnetic method, ground magnetometer surveys were made over several wells in two oil 

fields near Denver, Colo. Distinctive, monopolar-shaped 

anomalies having peak amplitudes of as much as several 

thousand nannoteslas (nT) were noted above the casings. 

The results were fit to appropriate pole-pair models by using 

a nonlinear least-squares algorithm. By means of the 

parameters determined from the ground data, modeling was 

carried out to determine suitable specifications for airborne 

measurements (Frischknecht and others, 1983). Airborne 

surveys were conducted over an oil field near Denver, 

Colo., and parts of four oil fields near Oklahoma City, 

Okla., to evaluate the usefulness of airborne surveys in 

locating wells. All of the surveys were made by using a 

flight height of 61 m and a flight-line spacing of 100m. A 

ground transponder-based microwave navigation system 

was used to provide the position of the aircraft within a few 

meters (Frischknecht and Raab, 1984; Frischknecht and 

others, 1985). 

Three independent sets of data were used in evaluating the effectiveness of the airborne surveys in Oklahomavisual and ground magnetometer observations at selected 

sites, a compilation of information from records, and results 

of an analysis of aerial photographs. Ground magnetometer 

measurements were made at sites where there was no 

obvious visual evidence of a casing to determine if there 

were hidden casings. Fairchild ( 1984) conducted a records 

search to determine the locations and specifications of all 

known wells in the areas surveyed. The available records 

Application of Geophysical Methods to the Study of Pollution Associated with Abandoned and Injection Wells 73 
did not give exact locations of wells, but they did provide 

estimates of the total number of wells in each section. Stout 

and Sitton (1984) identified probable locations of wells 

from analysis of several sets of aerial photographs taken at 

different times, the earliest set having been taken in the 

1930's. 

As an example of the results, an aeromagnetic contour map for part of Coon Creek field northeast of Oklahoma City is shown in figure 19 .1. Forty distinct magnetic 

features are labeled on the map; all features except No. 1, 

which is a negative anomaly, are believed to be caused by 

a single well or a cluster of wells. In section 3, which 

encompasses most of the area of figure 19.1 , the records 

search found 41 wells. The original photo analysis identified 36 probable wells in section 3, and the magnetic data 

indicate the presence of 39 wells. One well (I) was not 

detected by the airborne survey, probably because it occurs 

on the flank of a large anomaly ( 15, 15b) caused by other 

wells. Another such "hidden" well may account for the 

discrepancy between the results of the records search and 

the airborne results. A photographically identified well at 

III is not reflected in the contour map, but it caused 

distinctive anomalies of 4 and 5 nT in the aeromagnetic 

profiles along the nearest flight lines. One site, where there 

was a possible photographically identified well (II), was 

found not to contain a casing. The results for the Coon 

Creek field are fairly typical of all four test areas in 

Oklahoma. However, in most of the sections surveyed, the 

total number of magnetic anomalies that may be caused by 

casings exceeds the number found from records or estimated from aerial photographs. Magnetic methods should 

be equally effective in locating wells in other regions where 

conditions are similar to those in the Oklahoma test areas. 

In the test area in Colorado, tuffite beds or other 

magnetic material in the near-surface rocks caused shortwavelength anomalies that interfered with identification of 

anomalies from wells. However, evidence of most of the 

known wells and of one unknown well was found through 

examination of the aeromagnetic profiles rather than the 

contour maps. Ground checking was required to verify 

some of the interpretations. 

A pilot project was conducted in industrial and 

residential areas of Santa Clara County, Calif. , to explore 

the feasibility of locating abandoned water wells from 

analysis of historical aerial photographs and ground magnetic measurements. In this region, wells that were used for 

irrigation of orchards and other crops have been abandoned 

and covered over, and they are, in part, responsible for 

migration of chemicals from industrial spills into aquifers 

used for water supplies. Measurements over known water 

wells in the area showed that these wells produce magnetic 

anomalies of several hundred nannoteslas or more at the 

surface. ·In rural areas, such wells could easily be located by 

closely spaced ground magnetic measurements. At three 

sites, where photointerpretation by K. Stout (oral commun., 

1985) indicated the presence of wells, magnetic anomalies 

characteristic of casings were found. Characteristic anomalies were not found at six other photographically identified 

sites, possibly because the casings are gone. However, 

limited access to these sites due to buildings, streets, 

fences, and other urban structures and interfering magnetic 

anomalies from a host of steel objects including fences, 

lampposts, buildings, and automobiles made the use of the 

magnetometer difficult. Nevertheless, Jachens and others 

( 1986) concluded that ground magnetic methods can be 

effective tools in locating some of the wells in an urban 

environment. 

MAPPING BRINE CONTAMINATION 

As part of an EPA research program on methods for 

detecting and mapping fluids leaking from injection wells, 

transient electromagnetic soundings were made at two 

localities near Pawhuska, Okla., where brines have contaminated the surface (Fitterman and others, 1986). Zones of 

intense brine pollution have lower electrical resistivities 

than unpolluted regions containing fresher water. At one of 

the two test areas, brine has seeped out at the surface along 

fractures apparently caused by overpressuring a nearby 

injection well. Locations of electromagnetic soundings at 

this area are shown in figure 19.2; the squares are the 

outlines of the wire loop used for transmitting and receiving 

the transient electromagnetic signals (Raab and 

Frischknecht, 1985). As necessary, loops were laid out in 

an irregular pattern to avoid placing them directly over the 

numerous pipelines that exist in this field. 

The transient soundings were inverted by using a 

layered-earth model. Using such a model causes the interpreted results (fig. 19.3) to be somewhat in error locally 

where there are rapid lateral changes in the resistivity of the 

section. Nevertheless, a useful picture of variations in 

electrical resistivity can be obtained from this approach. 

Away from the polluted area, the field data were closely fit 

by a four-layer model. In the vicinity of known surface 

brine contamination, interpreted resistivities were generally 

lower, and the layering was disrupted, as shown in figure 

19.3. It is interesting to note that the resistivity of the upper 

layer has not been altered by the substantial brine seepage at 

the surface. 

Water samples taken from test drill hole No. 2 (fig. 

19.2) showed considerably higher salinities than those taken 

from Nos. 1 and 3 (Fitterman and others, 1986). Also, 

resistivities, as measured by induction logs, were lower in 

hole No. 1 than in holes No. 2 and 3, but they were not as 

low as expected from the surface soundings. Reasons for 

this discrepancy are not completely understood. 

In this example, surface electromagnetic soundings 

clearly outlined a zone of extreme brine pollution. Undoubt74 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
0 1000 

0 250 

2000 

feet 

500 

meters 

Figure 19.1. Aeromagnetic contour map over part of the 

Coon Creek oil fie ld northeast of Oklahoma City, Okla. 

Flight altitude was 61 m above terrain, line spacing was 

100 m, and contour interval is 2 nannoteslas. Magnetic 

edly, less intense pollution extends beyond the zone indicated in figure 19.3, but it cannot be detected because the 

resistivity of the unpolluted rocks in this area is very 

features discussed in text are labeled with Arabic numerals. Photographically identified holes not reflected in 

contour map are labeled with Roman numerals. 

low. However, relatively low concentrations of brine or 

other electrolytes can be detected and mapped in rocks that 

have higher resistivities. 

Application of Geophysical Methods to the Study of Pollution Associated with Abandoned and Injection Wells 75 
........ 

"' ... 

Cl> 

4i 

.§ 

c:: 

0 

iii 

> 

~ 

w 

R7E 

-·-·-·-·-·-·-·-·-·-·-·-·-·-·-·-·-·, 

Section 15 Section 14 

r·-·-·-·-·-·-·-·-r-·-·-----~~----~ 

' TDEM SUttons , a0 I I ,o V 

i [8J11 r.r.lr.l i 3 9 t 

· r- O.:,I.:J· ~ 1 I 1• 1

WELL 141 #1 WELL•#3 ~~ 15 I WELL #2 

I

·QI9 ·17 

~ I 16 ' 16 

I 

' Section 22 1 Section 23 

'---·-·-·-·-·-·-·1·---·-·---·-·-·-· 

0 1000 

0 METERS 

4000 

FEET 

OKLAHOMA 

T 26 N. 

..,. Figure 19.2. Location of electromagnetic soundings 

and test drill holes near Pawhuska, Okla. The squares 

are outlines of wire loops used for transmitting and 

receiving signals. Darkened squares overlie polluted 

regions. TDEM, time-domain electromagnetic method. 

Figure 19.3. Electrical sections interpreted from electromagnetic soundings . Regions of most intense brine pollution are indicated . Station numbers refer to locations on 

figure 19.2. TDEM, time-domain electromagnetic method; 

Om, ohm-m. 

TDEM Station Locations 

w 

300 

200 

100 

0 

Sa 

9 

3 10 12 13 

9-110m 

4-sOm :_-:aa·gi-\/": 

! 2-40m\ 

2- 3.50m 

0 

w 

... 

::: 

.... 

0 

0.. 

1.5- 2.5 Om 

15 E W E W 18 17 E 

~ ~ 

20 19 ... 16 

7 - 9 Om 

/ 6- 11Om 

1 .5-20m 

5b 5c 
Rt:t=ERI:NCES CITED 

Fairchild, D.M., 1984, Selection of flight paths for magnetometer 

survey of wells; Proceedings, 1st National Conference on 

Abandoned Wells-Problems and solutions: Norman, 

Okla., University of Oklahoma, Environmental and 

Groundwater Institute, p. 144-163. 

Federal Register, 1979, Proposed rules-Notices: Federal Register, v. 44, no. 78,p. 23738,23744,23746,23754,23755. 

Fitterman, D.V., Raab, P.V., and Frischknecht, F.C., 1986, 

Detection of brine contamination from injection wells using 

transient electromagnetic soundings: Environmental Protection Agency, Environmental Monitoring Systems Laboratory, 62 p. 

Frischknecht, F.C., Grette, Roger, Raab, P.V., and Meredith, J., 

1985, Location of abandoned wells by magnetic surveysAcquisition and interpretation of aeromagnetic data for five 

test areas: U.S. Geological Survey Open-File Report 

85-614-A, 64 p. 

Frischknecht, F.C., Muth, Lorant, Grette, Roger, Buckley, Thomas, and Kornegay, Burl, 1983, Geophysical methods for 

locating abandoned wells: U.S. Geological Survey OpenFile Report 83-702, 211 p. 

Frischknecht, F. C., and Raab, P. V., 1984, Location of abandoned 

wells by magnetic surveys; Proceedings, 1st National 

Conference on Abandoned Wells-Problems and solutions: 

Norman, Okla., University of Oklahoma, Environmental 

and Groundwater Institute, p. 186-215. 

Jachens, R.C., Webring, M.W., and Frischknecht, F.C., 1986, 

Abandoned-well study in the Santa Clara Valley, California: U.S. Geological Survey Open-File Report 86-0350, 

13 p. 

Raab, P. V., and Frischknecht, F. C., 1985, Investigation of brine 

contamination using time-domain electromagnetic soundings: U.S. Geological Survey Open-File Report 85-528, 

54 p. 

Stout, K.K., and Sitton, M.D., 1984, Locating abandoned oil and 

gas wells with historical aerial photos; Proceedings, 1st 

National Conference on Abandoned Wells-Problems and 

solutions: Norman, Okla., University of Oklahoma, Environmental and Groundwater Institute, p. 164-185. 

Application of Geophysical Methods to the Study of Pollution Associated with Abandoned and Injection Wells 77 

20. The Use of Spectroscopy in Environmental 

Geochemical Studies 

By Roger N. Clark and Trude V.V. King 

Most minerals show diagnostic absorption features in 

the reflected solar radiation part of the spectrum (0.3-2.5 

(~m) and in the thermal infrared part of the spectrum (8-14 

~m). These absorptions can be used to determine the 

mineralogy of the surface and, in a growing number of 

cases, the trace elements present in those minerals. Mineralogy can be determined over large areas by using a new 

generation of airborne or spacecraft instrumentation called 

mapping (or imaging) spectrometers that obtain spectral 

data for millions of points on the surface. 

Spectroscopy may prove to be a valuable environmental geochemical tool. Recent advances in laboratory 

studies of minerals at high spectral resolution have shown 

many narrow absorptions and fine structures not previously 

observed. As the absorptions are sensitive to the cation site 

locations, small changes in mineral chemistry may change 

the band positions. For example, iron can be detected at the 

parts-per-million level in most silicate minerals. It has 

recently been shown that nickel can be detected at the 

parts-per-thousand level in olivine (King, 1986), and manganese can be detected at the parts-per-thousand level and 

iron at the parts per million level in dolomite (Gaffey, 

1984). In calcite, it has been shown that copper can be 

detected at the parts-per-ten-thousand level (Gaffey, 1984). 

This aspect of spectroscopy may prove extremely valuable 

in monitoring the environment. In addition, recent highresolution studies of the magnesium-rich serpentine mineral 

group (King, 1986) have shown that it is possible to 

spectrally distinguish the isochemical end members 

chrysotile, lizardite, and antigorite (fig. 20.1). Other data 

show that spectral differences exist between the members of 

a solid solution series such as in tremolite-actinolite (fig. 

20.2). In some cases, instead of different absorptions 

appearing with compositional or structural changes, small 

changes in band position appear, as illustrated with sodium 

or calcium montmorillonite (fig. 20.3). 

In the last decade, remote-sensing instruments contained only a few spectral channels, but new mediumresolution spectroscopic instruments that have more than 

100 spectral channels are already being flight tested. These 

new instruments can resolve fairly narrow absorption features and possibly detect subtle changes in band width. The 

identification of absorption bands means that direct identification and mapping of mineral type can now be accomplished. The near-infrared spectral region is very sensitive 

to OH-bearing minerals, especially clays. Detection levels 

of clays can be better than 1 percent, depending on data 

quality. This new generation of remote sensing instruments 

has the potential for mapping mineral type and potentially 

toxic contaminants in minerals at the surface over large 

areas. Similarly, handheld spectrometers can be used in the 

field to perform the same identifications on hand samples 

from the surface, a borehole, or bottom sediments. 

The Use of Spectroscopy in Environmental Geochemical Studies 79 
". 95 

CHRYSOTLE 

. 90 

UZARDITE (rectilinear lattice) 

• 35 

• 3B 

ANTIGORITE (corrugated rectilinear 

• 25 lattice) 

1. 36 1.39 1.4B 1.42 

WAVELENGTH (urn) 

Figure 20.1. Near-infrared reflectance spectra of powdered chrysotile, lizardite, and antigorite. All three minerals have 

the same composition but different lattice structure. The small differences in structure cause slight differences in bond 

strengths of the OH radical and give different band positions and strengths. Spectra are at x 2 resolution. 

80 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
w 

u 

z 

< 

tu 

w 

_J 

l1. 

~ra.s 

1. a7 1. as 

Tremolite 

Actinolite 

1. as 1. 4fa 1. 41 1. 42 

WAVELENGTH C.Um> 

Figure 20.2. Near-infrared reflectance spectra of powdered tremolite and actinolite (composition Ca2 (Mg,Fe +2

)5 

Si80 22 (0Hb). The change in composition of this solid-solution series results in changes in the absorption bands. 

The Use of Spectroscopy in Environmental Geochemical Studies 81 
lJJ ufZJ.6 

z 

< tu 

lJJ 

...J 

11.. 

lJJ 

Q: 

• 4 

Sod i u m-montmori lion ite 

(SWy-1) 

1. 9 2. fZJ 

Calcium-montmorillonite 

(SAz-1) 

2. 1 2. 2 

WAVELENGTH <,um> 

Figure 20.3. Near-infrared spectra of a sodium montmorillonite (SWy-1) and calcium montmorillonite (SAz-1). Note the 

small shift in the absorption band position near 2.2 j.Lm. The CaO and Na2 0 contents are 1.68 percent and 1.53 percent, 

respectively, for SWy-1, and 2.82 percent and 0.063 percent, respectively, for SAz-1. 

REFERENCES CITED 

Gaffey, S .J., 1984, Spectral reflectance of carbonate minerals and 

rocks in the near infrared (0.35-2.55 j.Lm) and its applications in carbonate petrology: Honolulu, Hawaii, University 

of Hawaii, unpublished Ph.D. thesis. 

King, t.V. V., 1986, Contributions toward a quantitative understanding of reflectance spectroscopy-Phyllosilicates, olivine, and shocked materials: Honolulu, Hawaii, University 

of Hawaii, unpublished Ph.D. thesis. 

82 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
21. Application of Stable-Isotope Techniques to 

Environmental Geochemistry 

By Elliott C. Spiker 

SUMMARY 

Stable-isotope techniques have been successfully 

applied to a wide variety of environmental and geochemical 

problems. Natural processes have established recognizable 

patterns in the distribution of the stable isotopes of several 

light elements. Knowledge of these patterns and an understanding of how natural processes affect the isotopic distributions help to determine the sources and histories of these 

elements in many geologic systems. 

INTRODUCTION 

Most environmental isotope studies have focused on 

the stable isotopes of hydrogen ctH, 2

H), carbon ct 2C, 13C), 

nitrogen ct 4

N, 15N), oxygen ct 60, 180), and sulfur e2s, 34S). These elements are involved in most geochemical 

reactions and are the important elements in biological 

systems. Human activities, such as the application of 

agricultural fertilizers, the combustion of fossil fuels, and 

the disposal of organic wastes, are often accompanied by 

measurable isotopic changes in the affected environments. 

Stable-isotope techniques can be used to trace both the 

precursors and products of reactions. Although in complex 

situations the results can be ambiguous, stable isotopes can 

serve the important function of testing and eliminating 

hypotheses of geochemical reactions. Because many natural 

sources have variable isotopic compositions, the emphasis 

of most stable-isotope studies is on isotopic variations and 

comparisons within well-defined systems. Comprehensive 

reviews of the many applications of stable-isotope techniques are given in Jaeger and Hunziker (1979), Fritz and 

Fontes (1980), and Hoefs (1980). 

MINERAL AND WATER INTERACTIONS 

Variations in the isotopic composition of meteoric 

water are primarily due to evaporation and condensation 

processes that are related to temperature, altitude, and 

latitude. Knowledge of the global patterns of the isotopic 

composition of hydrogen and oxygen in meteoric water can 

be used to determine the source and history of water, the 

mixing of ground water and surface water, and the location 

of ground-water recharge areas. Fractionation of stable 

carbon isotopes among gaseous, aqueous, and solid phases 

can be used in conjunction with mathematical models to 

determine the geochemical evolution of a ground water and 

to identify different sources of inorganic carbon in the 

water. The mass balance of carbon and carbon isotopes may 

be used to make corrections to measured 14C ages of ground 

water. Also, the nitrogen isotopic composition of dissolved 

nitrate in surface and ground water can indicate the relative 

contributions of nitrogen from fertilizer and animal waste. 

The isotopic patterns in waters often are reflected in 

the isotopic composition of certain sedimentary materials in 

isotopic equilibrium with the water, such as carbonate 

minerals, silica, clays, and evaporite minerals. The oxygenisotope composition of these sedimentary minerals can be 

used to determine their formation temperature. The isotopic 

fractionations among water, C02 , and carbonate minerals 

have been thoroughly studied because of the abundance of 

carbonate minerals in sedimentary environments. 

Deep ground water may undergo oxygen-isotope 

exchange with aquifer rocks, particularly carbonate minerals, as depth and temperature increase. The resulting 

oxygen-isotope shifts in both the water and the rocks are 

then a useful indicator of this exchange process (for 

example, see Hearn and others, this volume). Such oxygen 

isotopic shifts may be large in hydrothermal systems. Stable 

carbon and oxygen-isotope compositions of carbonate minerals, in combination with an understanding of traceelement partitioning and textural changes during carbonate 

diagenesis, can provide information on the relative influences of meteoric or marine waters, sources of dissolved 

carbonate, changes in pore fluids, and the extent of rock and 

water interactions. 

Application of Stable-Isotope Techniques to Environmental Geochemistry 83 
SOURCE AND DIAGENESIS OF SEDIMENTARY 

ORGANIC MATTER 

Isotopic changes accompanying the decomposition of 

organic matter in anoxic sediments have been extensively 

studied. The microbial processes of sulfate reduction and 

methane production impart distinct isotopic signatures to 

the C02 and CH4 produced. The isotopic composition of 

various authigenic carbonate minerals associated with 

organic-rich sediments may record isotopic changes resulting from geochemical evolution of the pore water. 

The fate of pollutants adsorbed on particulate matter 

in aquatic systems is largely determined by the transport and 

deposition of these particulates. Stable carbon isotopes have 

been used in several studies as tracers of terrestrial organic 

matter in marginal marine environments (see reviews by 

Degens, 1969; and Deines, 1980). Carbon isotopes have 

also been used to estimate the contribution from estuarine 

algae to the organic matter in estuarine sediments (Spiker 

and Schemel, 1979; Spiker, 1981). Because of the complexity and variability of many of these systems, such 

studies require an understanding of the hydrology of the 

system and should be done in combination with other tracer 

techniques, such as elemental ratios (C:N) and lignin 

analysis (Hedges and Mann, 1979). 

Environmental studies of sedimentary organic matter 

need to include a consideration of the effects of decomposition and formation of humic substances. Studies using 

carbon isotopes and solid-state nuclear magnetic resonance 

techniques (Hatcher and others, 1983; Spiker and Hatcher, 

1984) indicate that the selective degradation of carbohydrates leads to a significant decrease in the 13C/ 12C ratio of 

the residual organic matter preserved in the sediment. These 

isotopic shifts are useful in the study of early diagenetic 

processes but must also be taken into account in isotopic 

tracer studies of sedimentary organic matter. 

SOURCES AND EFFECTS OF ANTHROPOGENIC 

SULFUR 

Assessment of man's contribution of sulfur compounds to the atmosphere is difficult because of natural 

variability; however, sulfur isotopes e4

S/ 32S) promise to be 

very useful. Combustion of fossil fuels may produce sufficient sulfur oxides to significantly alter the isotopic composition of sulfur in sediments, soils, plants, and water. 

Studies of 34S in rainfall have shown pronounced isotopic 

shifts in industrial areas (Krouse, 1980). Such effects are 

only beginning to be studied and offer great potential for 

environmental studies (for example, see Gough, this volume). Sulfur isotopes may prove useful in studies of acid 

rain and the role of atmospheric sulfur oxides in the 

dissolution of building stone. Our preliminary studies indicate that 34S in the gypsum-rich crust that forms on the 

surface of exposed stone may distinguish atmospheric sulfur 

from sulfate that may be found naturally in the stone. 

The formation of acid waters by the oxidation of 

pyrite-bearing ore deposits, mine tailings, and coal strata is 

a complex and serious environmental problem. These 

sources of sulfur may be distinguished isotopically from 

sulfate from evaporite minerals, the most common natural 

source of sulfate in surface waters. The sulfur and oxygen 

isotopic composition of sulfur compounds in surface waters 

can also give information on important biochemical transformations, such as the role of bacteria in pyrite oxidation 

(Taylor and others, 1984). 

CONCLUSIONS 

Stable-isotope techniques can be applied to a variety 

of environmental problems where they serve as tracers and 

as parameters for testing hypotheses of geochemical and 

biochemical reactions. These environmental studies benefit 

greatly from the large amount of information available 

concerning the geochemistry and global distribution patterns of the light elements and their isotopes. This information provides a context for the analysis of anthropogenic 

effects. Stable-isotope techniques are most successful when 

applied in conjunction with other techniques in a multidisciplinary fashion. 

REFERENCES CITED 

Degens, E.T., 1969, Biogeochemistry of stable carbon isotopes, 

in Eglington, G., and Murphy, M.T.J., eds., Organic 

geochemistry: Berlin, Springer-Verlag, p. 304-329. 

Deines, P., 1980, The isotopic composition of reduced organic 

carbon, in Fritz, P., and Fontes, J.Ch., eds., Handbook of 

environmental isotope geochemistry, v. 1.: Amsterdam, 

Elsevier Scientific, p. 329-406. 

Fritz, P., and Fontes, J.Ch., 1980, Handbook of environmental 

geochemistry, v. 1.: Amsterdam, Elsevier Scientific, 

545 p. 

Hatcher, P.G., Spiker, E.C., Szeverenyi, N.M., and Maciel, 

G.E., 1983, Selective preservation-The origin of 

petroleum-forming aquatic kerogen: Nature, v. 305, 

p. 498-501. 

Hedges, J.I., and Mann, D.C., 1979, The lignin geochemistry of 

marine sediments from the southern Washington coast: 

Geochimica et Cosmochimica Acta, v. 43, p. 1809-1818. 

Hoefs, Jochen, 1980, Stable isotope geochemistry (2d ed.): New 

York, Springer-Verlag, 208 p. 

Jaeger, E., and Hunziker, J.C., eds., 1979, Lectures in isotope 

geology: Berlin, Springer-Verlag, 312 p. 

Krouse, H.R., 1980, Sulfur isotopes in our environment, in Fritz, 

P., and Fontes, J.Ch., eds., Handbook of environmental 

isotope geochemistry: Amsterdam, Elsevier Scientific, 

p. 435-471. 

Spiker, E.C., 1981, Carbon isotopes as indicators of the source 

and fate of carbon in rivers and estuaries, in Carbon dioxide 

effects research and assessment program-Flux of organic 

carbon by rivers to the oceans; report of a workshop, 

Woods Hole, Mass., SepL 21-25, 1980: U.S. National 

84 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Technical Information Service Report No. CONF8009140, p. 75-108. 

Spiker, E.C., and Hatcher, P.G., 1984, Carbon isotope fractionation of sapropelic organic matter during early diagenesis: 

Organic Geochemistry, v. 5, p. 283-290. 

Spiker, E. C., and Schemel, L.E., 1979, Distribution and stable 

isotope composition of carbon in San Francisco Bay, in 

Conomos, T.J., San Francisco Bay, the urbanized estuary: 

San Francisco, Pacific Division, American Association for 

the Advancement of Science, p. 195-210. 

Taylor, B.E., Wheeler, M.C., and Nordstrom, D.K., 1984, 

Isotope composition of sulphate in acid mine drainage as 

measure of bacterial oxidation: Nature, v. 308, no. 5959, 

p. 538-541. 

Application of Stable-Isotope Techniques to Environmental Geochemistry 85 

22. Quaternary Geology and Pollution ProblemsAn Example from the San Francisco Bay Area, 

California 

By Ed Helley 

Geologic maps that emphasize engineering properties 

of surficial deposits provide much needed information 

pertaining to the areal distribution of sediment, including 

grain size, porosity, and permeability. These parameters 

govern the movement of ground water and are critical in 

predicting the probable migration rates and pathways of 

plumes of toxic waste. Mapping in urbanized terranes, 

however, poses several problems for the geologist, as most 

of the landscape is paved or graded and covered by urban 

sprawl. Specialized mapping techniques have been devised 

that enable the geologist to depict the geology in spite of the 

deleterious effects of urban development. 

One such area, for example, that has not only 

undergone rapid growth but also has a severe pollution 

problem is the flatland region of south San Francisco Bay, 

a structural valley often referred to as Silicon Valley, the 

locus of a multibillion dollar electronic and semiconductor 

industry. Figures 22.1 and 22.2 illustrate the changing 

character of the valley floor from 1959 (chiefly orchards) to 

1977 (chiefly urban). In 1986, the floor of the valley is even 

more densely urbanized. 

A complex water supply system serves the south San 

Francisco Bay and its nearly 2 million residents. Water for 

municipal and industrial uses comes from ground water, 

impounded surface water, and surface water imported from 

the Sierra Nevada through San Francisco's Hetch Hetchy 

and South Bay Aqueducts. Ground water supplies more 

than half the region's drinking water. Therefore, avoiding 

contamination of the aquifers with toxic waste is vitally 

important. However, toxic wastes continue to threaten 

potable ground-water reservoirs. At present at least 100 

contaminated sites are known in Silicon Valley. For example, in late 1981, a leak was discovered in underground 

storage tanks located at Fairchild Camera and Instrument 

Company in southern San Jose. The inventory and disposal 

records revealed that 60,000 gallons of solvent (trichloroethane or TCE) had been lost over an 18-month period. Some 

municipal wells situated down the hydraulic gradient were 

found to contain as much as 8, 800 parts per billion (ppb) 

TCE (California Department of Health Services, 1984). 

The U.S. Geological Survey is eminently qualified to 

provide information of pathways of toxic wastes in Silicon 

Valley. Helley and others ( 1979) mapped the geology of the 

flatlands of the bay region by using several innovative and 

specialized mapping techniques. The alluvial units were 

defined by geologic criteria, including depositional environment, geomorphic expression, soil-profile development, 

age, induration, compaction, and grain-size distribution. 

The distribution of geologic map units was determined from 

documents that predate urban development, such as topographic maps, soil maps published by the U.S. Department 

of Agriculture, and aerial photographs. Although soil maps 

were used to help construct the geologic map, the geologic 

map describes greater thicknesses than the uppermost 5 to 6 

feet, an extrapolation largely based on the process by which 

the deposit was laid down. The depositional processes are 

influenced by active tectonism, climate change, and changing sea level caused by melting of continental glaciers. 

Sometimes very old topographic maps, in this case 

one from 1895, can aid in differentiating pristine topographic features. For example, flood basins can be distinguished from alluvial fans or levees or tidal marshes. 

Figures 22.3, 22.4, 22.5, and 22.6 illustrate for a small area 

near Palo Alto, Calif., the kinds of maps used in compilations of an environmental geologic map for the San Francisco Bay region (Helley and others, 1979). 

On the basis of relative soil-profile development, 18 

alluvial soil series that were described by the Soil Conservation Service (1968) (fig. 22.4) were grouped by Helley 

and others ( 1979) into two distinct groups that reflect 

fundamental differences in the deposits in which they are 

developed. The soil units that have strongly developed 

weathering profiles constitute one group, and those that 

have weakly developed weathering profiles constitute 

another. The alluvial deposits characterized by strongly 

developed weathering profiles are inferred to be significantly 

Quaternary Geology and Pollution Problems-An Example from the San Francisco Bay Area, California 87 
Figure 22.1. Aerial photograph of Silicon Valley, Calif., taken in 1959. Note agricultural character of the valley. 

88 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Figure 22.2. Aerial photograph of Silicon Valley, Calif., taken in 1977. Note urban character of the valley. 

Quaternary Geology and Pollution Problems-An Example from the San Francisco Bay Area, California 89 
'r c.::./ 

37°22'30" -- ~~----~~~~-- --~~~~~~~~~~-L~--~----~~~----~~--~==~~~--~ 

Figure 22.3. Alluvial deposits related to geologic processes in the Palo Alto area, California. The enhanced 

contour lines reveal the fluvial geomorphic features, alluvial fans, natural stream levees, and flood basins on the 

broad alluvial plain between the bay marshlands and the 

irregular bedrock uplands. Distribution of former tidal 

marshland from Nichols and Wright (1971). Base map from 

U.S. Geological Survey, Mountain View (1961, photorevisions as of 1973), Newark (1959, photorevisions as of 

1973), Palo Alto (1961, photorevisions as of 1973), and 

Redwood Point (1959, photorevisions as of 1973) 1 :24,000-

scale quadrangles. From Helley and others (1979). 

90 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
older than the deposits that have weak profiles. These two 

groups of deposits therefore simply indicate younger and 

older alluvial deposits. 

The younger deposits constitute the alluvial fans 

formed under the present climatic regime. The present 

streams forming these younger fans are graded to present 

sea level. The older alluvial deposits now partly covered by 

the younger (Holocene) deposits make up alluvial fans 

formed by these same streams when they were graded to 

lower stands of sea level during the Wisconsinan glacial 

maxima about 18,000 years ago. At that time, sea level was 

lower by about 330 to 420 ft, and the Pacific shoreline was 

near the Farallon Islands some 36 mi west of the Golden 

Gate (Atwater and others, 1977). The Holocene alluvium is 

differentiated further into depositional facies on the basis of 

textural characteristics of surface soils; that is, the relative 

proportions of gravel, sand, silt, and clay. These textural 

data were obtained chiefly from published soil reports and 

unpublished engineering foundation reports for roads, 

bridges, and other structures. In addition, these deposits are 

differentiated by depositional environments (such as levees 

and flood basins) determined from geomorphic expression 

as shown on old topographic maps and aerial photographs. 

These stream deposits grade into and interfinger with 

fine-grained silt and clay deposits that form the flat floor of 

the alluvial flood basins between stream levees on the outer 

margins of the alluvial fans directly adjacent to the bay 

marshlands. The fine-grained basin deposits interfinger 

with and grade into the bay mud-the carbonaceous, wet 

silty clay that was deposited into the marshes and mudflats 

of San Francisco Bay as sea level rose as a result of the 

melting of glacial ice. The landward extent of the bay mud 

underlying former marshes and mudflats of San Francisco 

Bay was established from early (about 1850) U.S. Coast 

and Geodetic hydrographic charts (Nichols and Wright, 

1971) rather than from direct field observation, because 

human activity over the past 100 years has obscured its 

original distribution. 

Fossils, archaeological remains, and radiometric ages 

of deposits corroborate the relative ages and correlations 

based on these limited geographic and soils data. The upper 

part of the Pleistocene alluvial unit contains a (Rancholabrean) fossil vertebrate fauna consisting mainly of extinct 

species-camel, horse, bison, mammoth, and ground sloth. 

However, the Holocene alluvial deposits contain a fossil 

fauna that has a completely modern aspect (deer and elk). 

When the late Pleistocene alluvial-fan drainages were 

graded to rivers that, in turn, were graded to a lower sea 

level, drainage channels were cut into older Pleistocene 

deposits. During the Holocene transgression of San Francisco Bay, these older channel deposits were buried by the 

encroaching bay mud and by early Holocene alluvium. 

These fossil channels today serve as conduits through which 

ground water moves downslope; these channels are numerous and comprise stringer aquifers. 

The surficial mapping techniques described here will 

allow mapping of urbanized terranes, help geologists to 

predict where toxic waste is likely to travel, and indicate 

what surface areas are especially vulnerable to rapid infiltration of toxic fluids. 

The U.S. Geological Survey should have an active 

role in such work, as it has already produced surficial maps 

of large areas of our country. For example, Helley and 

Harwood ( 1985) have completed such a map of the entire 

Sacramento Valley in California. 

Quaternary Geology and Pollution Problems-An Example from the San Francisco Bay Area, California 91 
Figure 22.4. Soil units in Palo Alto area, California. Soil 

units are defined primarily on the basis of profile development, texture, and slope. Soil profile development is 

controlled by many factors including time, climate, parent 

material, slope, and biological activity. In this area where 

weathering conditions and parent material are relatively 

uniform, the time factor is clearly expressed by relative 

soil-profile development, which can therefore be used as 

a means of differentiating alluvial deposits on the basis of 

relative age. The symbols shown on the map refer to the 

names of local soil series (Soil Conservation Service, 

1968). Base map from U.S. Geological Survey Mountain 

View (1961, photorevisions as of 1973), Newark (1959, 

photorevisions as of 1973), Palo Alto (1961, photo revisions 

as of 1973), and Redwood Point (1959, photo revisions as of 

1973) 1 :24,000-scale quadrangles. From Helley and others 

(1979). 

92 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
EXPLANATION 

Soil Series in the Palo Alto area* 

Alluvial soil series with weakly to moderately developed weathering profiles: 

An Alviso clay 

8a 8ayshore clay 

Ca Campbell silty clay loam 

Cc Campbell silty clay loam, clay substrate 

Ch Clear Lake day, drained 

Cr A Cropley day; 0- to 2-percent slopes 

CrC Cropley clay; 2- to 9-percent slopes 

Csa Cropley day loam; 0· to 2-percent slopes 

GbB Garretsnn gravelly loam; 0- to 5-percent slopes 

Pf Pacheco loams, clay substrate 

Sv Sunnyvale silty day, drained 

YaA Yolo loam; 0- to 2-percent slopes 

YeA Yolo silty clay loam; 0- to 2-percent slopes 

Ys Yolo loam; no slope given, taken from older survey 

ZbA Zamora silty clay loam; 1- to 3-percent slopes 

ZbC Zamora clay loam; 2- to 9-percent slopes 

Zbz Zamora clay loam; 0- to 2-percent slopes 

Alluvial soil series with strongly developed weathering profiles: 

PoA Pleasanton loam; 0- to 2-percent slopes 

PoC Pleasanton clay loam; 0- to 2-percent slopes 

PpA Pleasanton gravelly loam; 0- to 2-percent slopes 

PpC Pleasanton gravf'lly clay loam; 2- to 9-percent slopes 

RaC Rincon clay loam; 0- to 2-percent slopes 

RaC2 Rincon clay loam; 2- to 9-percent slopes 

SdA San Ysidro loam; 0- to 2-percent slopes 

SdB San Ysidro loam; 2- to 9-percent slopes 

SdB2 San Ysidro loam; 2- to 9-percent slopes, eroded 

Upland soil series (nonalluvial soils): 

AvO Azule silty clay laom; 2- to 9-percent slopes 

AvD2 Azule silty clay loam; 9- to 15-percent slopes 

AvE Azule silty clay loam; 15- to 30-percent slopes 

DaA Diablo clay; 0- to 2-percent slopes 

DaC Diablo clay; 2- to 9-percent slopes 

DaE Diablo clay; 15- to 30-percent slopes 

GeE Gaviota loam; 15- to 30-percent slopes 

GoD Gilroy clay loam; 5- to 15-percent slopes 

GoE Gilroy clay loam; 15- to 30-percent slopes 

GmE Gaviota-Los Gatos complex; 15- to 30-percent slopes 

LgE Los Gatos clay loam 

LoE Los Osos clay loam; 15- to 30-pcrcent slopes 

Lkg3 Los Gatos and Mayrncn complex; 50- to 75-percent slopes 

Lt IJ Los Trancos stony clay; 15- to 30-percent slopes 

PrC Positas-Saratoga loam; 2- to 9-perccnt slopes 

ShE Soper gravelly loam 

SgC Saratoga-Positas loam; 2- to 9-pcrcent slopes 

Miscellaneous map symbols: 

KfH Kitchen middens, archeolo~icaf site 

PkG Gravel pits 

Tf Tidal mudflats 

*From U.S. Soil Conservation Service (1968) 

Quaternary Geology and Pollution Problems-An Example from the San Francisco Bay Area, California 93 
37"22'30" 

Figure 22.5. Distribution of younger and older alluvial 

deposits in the Palo Alto area, California, as determined 

primarily from relative soil-profile development of soil 

series as mapped by Soil Conservation Service (1968). 

Alluvial deposits on which weak to moderate weathering 

profiles are developed were initially inferred to be 

younger than alluvial deposits on which strong weathering profiles are developed. Radiocarbon and fossil data 

have confirmed this relative age classification. The 

younger alluvial deposits contain modern vertebrate and 

invertebrate fossils and organic remains that yield radioEXPLANATION 

Younger undeveloped soils 

. ' . Older well-developed soils 

Upland soils I 

carbon ages of about 5,000 years ago and younger. The 

older alluvial deposits locally contain extinct late Pleistocene vertebrate fossils, such as camel , sloth, bison, and 

mastodon, and organic remains that yield radiocarbon 

ages of about 20,000 years. Base map from U.S. Geological Survey Mountain View (1961 , photo revisions as of 

1973), Newark (1959, photorevisions as of 1973), Palo Alto 

(1961 , photorevisions as of 1973), and Redwood Point 

(1959, photorevisions as of 1973) 1 :24,000-scale quadrangles. From Helley and others (1979). 
122°10' 

r 

37°30' "< ... , ~~:~.: 

Qhbm 

37°27'30'' 

37°25 ' 

Figure 22.6. Surficial geologic map of the Palo Alto area, 

California. The symbols shown on the map refer to the 

names of local surficial and bedrock units. Dashed and 

dotted lines indicate drainages. Base map from U.S. 

Geological Survey Mountain View (1961, photorevisions 

as of 1973), Newark (1959, photorevisions as of 1973), 

Palo Alto (1961, photo revisions as of 1973), and Redwood 

Point (1959, photorevisions as of 1973) 1 :24,000-scale 

quadrangles. From Helley and others (1979). 

Quaternary Geology and Pollution Problems-An Example from the San Francisco Bay Area, California 95 
Description of Map Units 

Holocene deposits (less than 10,000 years old): 

Estuarine deposits (0-9,000 years old): 

Qhbm Bay mud. Water-saturated estuarine mud; predominantly clay and silty clay underlying marshlands 

and tidal mudflats of San Francisco Bay. Contains 

a few lenses of well-sorted fine sand and silt and a 

few shelly and peaty layers. Interfingers with and 

grades into fine-grained and medium-grained alluvium; generally overlies early Holocene alluvium or 

late Pleistocene alluvium 0-120 ft (0-40 m) thick. 

Alluvial deposits (0-5,000 years old): 

Qhaf Fine-grained alluvium. Plastic, poorly sorted carbonaceous clay and silty clay in poorly drained interfluvial basins marginal to bay marshlands. Locally 

contains thin beds of well-sorted silt, sand, and fine 

gravel; contains modern vertebrate fossils and 

fresh-water gastropod and pelecypod shells. Interfingers with and grades into bay mud and mediumgrained alluvium; overlies late Pleistocene alluvium. Generally less than 15 feet (5 m) thick. 

Qhafs Salt affected fine-grained alluvium; same as Qhafbut 

containing high concentration of salt. 

Qham Medium-grained alluvium. Loose, moderately 

drained, moderately sorted sand forming alluvial 

plains and stream levees. Locally contains beds of 

well-sorted clay, silt, and gravel; contains modern 

vertebrate fossils and fresh-water gastropod and 

pelecypod shells. Intermediate in character and 

lateral extent between fine-grained and coarsegrained alluvium with which it interfingers; generally overlies late Pleistocene alluvium. Generally 

less than 21 feet (7 m) thick. 

Qhac Coarse-grained alluvium. Loose well-drained, moderately sorted, permeable sand and gravel forming 

stream levees and flood plains on higher parts of 

Figure 22.6-Continued. 

REFERENCES CITED 

Atwater, B.F., Hedel, C.W., and Helley, E.J., 1977, Late Quaternary depositional history, Holocene sea-level changes, 

and vertical crustal movement, southern San Francisco 

Bay, California: U.S. Geological Survey Professional 

Paper 1014, 15 p. 

California Department of Health Services, 1984, Ground water 

and drinking water in the Santa Clara Valley: A White 

Paper, coauthored with California Regional Water Quality 

Control Board No. 2, Santa Clara County Public Health 

Department, Santa Clara Valley Water District, and the 

U.S. Environmental Protection Agency, 66 p. 

Helley, E.J., and Harwood, D.S., 1985, Geologic map of the late 

Cenozoic deposits of the Sacramento Valley and Northern 

alluvial fans; gravel becomes dominant toward fan 

heads. Locally contains beds of well-sorted silt, 

sand, and gravel; contains modern vertebrate 

fossils and fresh-water pelecypod and gastropod 

shells. Thickness ranges from as much as 50feet(15 

m) at fan heads to 20 feet (6 m) where these deposits 

interfinger with and grade into medium-grained 

alluvium; overlies late Pleistocene alluvium and 

bedrock. 

Pleistocene deposits (10,000-3,000,000 years old): 

Qpa Late Pleistocene alluvium (10,000-70,000? years old). 

Weathered, slightly consolidated and indurated 

alluvial fan deposits consisting primarily of gravel 

and sand with some silt. Less permeable than 

Holocene alluvium. Locally contains fresh-water 

pelecypod and gastropod shells and extinct late 

Pleistocene vertebrate fossils. Overlain by Holocene deposits on lower parts of alluvial plain; incised by channels thatere partly filled with Holocene alluvium on higher parts of alluvial plain. 

Maximum thickness unknown but at least 150 feet 

(45 m) near margins of present bay where these 

deposits overlie deeply buried Pleistocene estuarine 

deposits. 

Bedrock: 

Qpea Early Pleistocene and Pliocene alluvium. Tectonically deformed alluvial-fan deposits with local minor amounts of shallow-water marine deposits. 

Weakly to moderately indurated gravel, sand, and 

silt with subordinate amounts oflacustrine silt and 

clay; local thin tuff beds; contains late Pliocene and 

early Pleistocene vertebrate fossils. Underlies late 

Pleistocene alluvium; overlies or in fault contact 

with Franciscan Formation. Consists of the Santa 

Clara Formation in southwest bay area. 

Br Undifferentiated Tertiary bedrock. Well-indurated 

sandstone, shale, and volcanic rocks. In map area 

underlies or is in fault contact with Pliocene and 

early Pleistocene alluvium. 

Sierran foothills, California: U.S. Geological Survey Miscellaneous Field Studies Map MF-1790, scale 1:62,500. 

Helley, E.J., Lajoie, K.R., Spangle, W.E., and Blair, M.L., 

1979, Flatland deposits of the San Francisco Bay region, 

California-Their geology and engineering properties and 

their importance to comprehensive planning: U.S. Geological Survey Professional Paper 943, 88 p. 

Nichols, D.R., and Wright, N.A., 1971, Preliminary map of 

historic margins of marshland, San Francisco Bay, California: U.S. Geological Survey Open-File Report 71-216, 

scale 1 : 125,000. 

Robinson, G.D., and Spieker, A.M., 1978, Nature to be commanded .... : U.S. Geololgical Survey Professional Paper 

950, 95 p. 

Soil Conservation Service, 1968, Soils of Santa Clara County: 

Morgan Hill, Calif., U.S. Department of Agriculture, 

217 p. 

96 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
23. Toward a Capability for Predicting Transport of 

Sediments on the Continental Shelf and Slope 

and in Submarine Canyons Along the Northeast 

Coast of the United States 

By Bradford Butman 

For the last 10 years, the U.S. Geological Survey, in 

cooperation with the U .S. Minerals Management Service, 

has made extensive observations of currents and sediment 

movement along the East Coast of the United States. 

Measurements using moored current meters and special 

bottom-mounted instrument systems (Butman and Folger, 

USGS INSTRUMENT LOCATIONS 

42• 

41° 

40• 

39° 

1979; Strahle and Butman, 1985) were made on the 

continental shelf from 1975 to 1982 (fig. 23.1A); in 

Lydonia and Oceanographer Canyons from 1980 to 1982 

(fig. 23.18); and on the outer shelf and upper slope from 

1982 to 1984 (fig. 23.1 C). The long-range objective of this 

ongoing research is to provide a regional description of the 

• CURRENT 

0 TRIPOD 

A WIND 

BATHYMETRY IN METERS 

NAUT ICAL MILES 

0 

KILOMETERS 

Figure 23.1. A, Location of instruments deployed on the continental shelf between 1975 and 1982. Stations A, K, Q, and 

MB were maintained as long-term stations (for 2 to 4 years), while the other stations were occupied for 1 to 6 months as 

part of shorter term experiments. Base map modified from Uchupi (1968). 

Toward a Capability for Predicting Transport of Sediments 97 
68°201 68°101 68°001 

USGS CANYON MOORINGS 

40°40' • CURRENT 

D,. DEEP INSTRUMENT PACKAGE 

0 SHALLOW TRIPOD 

() BOTTOM PRESSURE 

40°30' 

OOCA 

OCB&. 

o}"J~ 

40°20' 

Figure 23.1. B, Location of instruments deployed in and 

around Lydonia and Oceanographer Canyons as part of 

the Canyon Dynamics Experiment conducted from 1980 to 

1982. Stations LCA, LCB, and LCI were maintained as 

physical oceanography and associated sediment movement. 

Knowledge of where and how fast sediment is transported 

can be used to plan monitoring studies, to evaluate possible 

environmental consequences of man's activity on the Outer 

Continental Shelf, and to understand the present distribution 

of surface sediments. Of special interest are the transport 

and ultimate fate of fine-grained sediments, to which 

man-induced pollutants readily adhere, and of drill muds 

and cuttings. 

The present focus of this program is the analysis and 

synthesis of the large data set. Analysis of the measurements made in the canyons and on the slope is expected to 

continue through 1989. Papers describing the mean circulation on Georges Bank (Butman and others, 1982, 1983; 

Butman and Beardsley , 1987; Butman and others, 1987); 

sediment transport in the Middle Atlantic Bight (Butman 

and others, 1979) and on Georges Bank (Bothner and 

others, 1981; Twichell and others, 1981, 1987; Butman and 

Moody, 1983; Twichell, 1983a; Butman, 1987); and the 

low-frequency currents (Noble and others, 1983, 1985), the 

67"50' 

LCMf!l 

67"40' 67°30' 

0MOBIL BLOCK 

312 

f!JLCA 

LC f!JLCL 

<:::.. 

%_ £LCI 

LCN '? 

LCG• • • co •LCJ 

LCF ~ 

•LCK 

~ 

£LCH 

0 10 

I ' I " I ' I I I I 

km 

long-term stations, while the other stations were occupied 

for 1 to 6 months as part of shorter term experiments. 

Bathymetry from National Ocean Survey Charts 13203 and 

13204. 

tidal currents (Moody and others, 1984), and the geology 

and bathymetry of Lydonia Canyon (Twichell, 1983b; 

Butman and Moody, 1984) have been published. These 

analyses provide a description of the physical oceanography 

of the region, which is essential background for regional 

studies of sediment transport. 

The observations show that sediment movement of 

varying intensity is caused by several processes that affect 

different regions of the continental margin for various 

lengths of time . Over iong periods of time, these intermittent transport events determine the distribution of sediments 

on the sea floor. On the crest of Georges Bank, the strong 

tidal currents cause nearly continuous sediment movement 

and, in concert with the westward residual flow, cause a net 

westward transport of fine-grained sediment along the south 

flank of Georges Bank toward the Middle Atlantic Bight. 

An area of fine-grained sediment on the shelf south of Cape 

Cod is a major modem sediment deposit along this transport 

pathway (fig. 23.2). Storms, particularly in winter, cause 

intense transport of fine-grained material back and forth 

98 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
60~ 

72° 71° 

, • ),.NANTUCKET '<2f:J ISLAND 

. NANTUCKET 

51/0ALS 

"' ..,. 

~ 

~ 

7o• 

= 

~ 

3o0°"' 

69° 

""- "' ~ ~ 

~ 

68° 67" 

U~GS 

SLOPE STATIONS 

"- LONGTERM 

• ARRAY 

0 25 50 

66° 

kilometers 

65° 

Figure 23.1. C, Location of instruments deployed on the outer shelf and slope between 1982 and 1984 as part of the Slope 

Experiment. Stations SA and SE were maintained as long-term stations. Base map modified from Uchupi (1968). 

along the shelf, primarily parallel to the shelf edge. On the 

crest of Georges Bank, this episodic movement by storms is 

in addition to the nearly continuous movement by the tidal 

currents. However, over the rest of the bank in water deeper 

than about 60 m and on the shelf in water depths less than 

about 100 m, storms are the most important cause of 

sediment resuspension . During storms, the oscillatory currents associated with surface waves are principally responsible for increasing the bottom stress above the level 

required for movement to occur, whereas net transport is 

caused by the quasi-steady wind-driven flows. Because the 

near-bottom currents caused by waves decrease rapidly with 

water depth, sediment resuspension by waves is more 

intense in shallower water. The relative rates of net sediment transport caused by storms and by the tidal currentmean flow process described above remains to be determined. 

Analysis of the observations made on the slope and in 

the submarine canyons is not complete; thus only preliminary results are available (Butman , 1988a,b; Csanady and 

others, 1988). On the outer edge of the shelf, a slight mean 

near-bottom off-shelf flow, coupled with strong currents 

associated with internal waves and Gulf Stream warm-core 

rings, winnows sediments from the shelf break. In the large 

submarine canyons, strong currents apparently caused by 

internal tides cause intense sediment movement. The net 

direction of bedload transport along the axis of the canyons 

caused by these flows may be upcanyon or downcanyon, 

and the observations show that the strength of the flow 

varies from canyon to canyon. There is apparently little 

sediment movement caused by currents on the continental 

slope in water deeper than about 300 m. 

These observations made in different physiographic 

regions of the margin provide a framework for assessing the 

extent and direction of modem sediment transport on a 

regional basis and for predicting the ultimate fate of 

material introduced onto the margin. Because the oceanographic processes that transport sediments vary throughout 

the Georges Bank region, the fate of material will depend 

on its physical characteristics (size and density) and on 

Toward a Capability for Predicting Transport of Sediments 99 
71" 70" 69" 

Figure 23.2. Summary diagram of tidal currents (twoheaded crossed arrows represent the tidal ellipse) and 

mean currents (bold arrows) on Georges Bank, Nantucket 

Shoals, and the southern New England shelf. Shaded area 

where the material is introduced. The observations suggest 

rapid dispersal of fine sediment (silts and clays) introduced 

onto the crest of Georges Bank and dispersal and westward 

transport of fine sediment introduced onto the south flank. 

Bedload transport of coarser sand-sized sediments is probably also slightly westward and offbank. On the open slope 

in water deeper than 300 m, sediments that reach the sea 

floor will probably remain for long periods of time. 

REFERENCES CITED 

Bothner, M.H., Spiker, E.C. , Johnson, P.P., Rendigs, R.R., and 

Aruscavage , P.J., 1981 , Geochemical evidence for modern 

sediment accumulation on the continental shelf off southern New England: Journal of Sedimentary Petrology, v. 51, 

p. 281-292. 

Butman, Bradford, 1987, Physical processes causing surficialsediment movement, chap. 13 , in Backus, R.H., ed., 

6s• 67" 

Tidal current: 

Mean current: 

Speed 20 em/sec 

500 km 

30 day displocement 

0 Extent of fine -grained deposits 

- Area where ufoce sediments contain more than 30% silt ptus clay 

0 25 50 miles 

0 25 50 kilometers 

Bathymetry In meters 

66" 65" 

is the location of the fine-grained sediment deposit; note 

the decrease in the strength of the tidal currents over this 

deposit. From Twichell and others (1981). 

Georges Bank: Cambridge , Mass. , M.I.T. Press, 

p. 147-162. 

---1988a, Downslope Eulerian mean flow associated with 

high-frequency current fluctuations observed on the Outer 

Continental Shelf and upper-slope along the northeastern 

U.S. continental margin-Implications for sediment transport: Continental Shelf Research , v. 8, p. 811-853. 

-ed., !988b, The North Atlantic slope and canyon study: 

Final report to U.S. Minerals Management Service under 

Interagency Agreement IA14-12-000J-30180: U.S. Geological Survey Open-File Report 88-27, 2 v., 625 p. 

Butman, Bradford, and Beardsley, R.C., 1987, Long-term observations on the southern flank of Georges Bank, pt. I, 

Seasonal cycle of current, temperature , stratification and 

wind stress: Journal of Physical Oceanography, v. 17, 

p. 367-384. 

Butman, Bradford, Beardsley, R.C. , Magnell, B. , Frye, D., 

Vermersch, J.A., Schlitz, R., Limeburner, R., Wright, 

W.R., and Noble . M.A., 1982, Recent observations of the 

mean circulation on Georges Bank: Journal of Physical 

Oceanography, v. 12, p. 569-591. 

100 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Butman. Bradford, and Folger, D.W., 1979, An instrument 

system for long-term sediment transport studies on the 

continental shelf: Journal of Geophysical Research. v. 84, 

p. 1215-1220. 

Butman, Bradford, Loder, J.W., and Beardsley, R.C., 1987, The 

seasonal mean circulation-Observation and theory, chap. 

11, in Backus, R.H., ed., Georges Bank: Cambridge, 

Mass., M.I.T. Press, p. 125-138. 

Butman, Bradford, and Moody, J .A., 1983, Observations of 

bottom currents and sediment movement along the U.S. 

East Coast continental shelf during winter, chap. 7, 60 p. in 

McGregor, B.A., ed., Environmental geologic studies on 

the United States Mid and North Atlantic Outer Continental 

Shelf area, 1980-1982, v. III, North Atlantic region: Final 

Report to Minerals Management Service, Vienna, Va., 

Available from National Technical Information Service, 

accession no. PB848187954. 

---1984, Bathymetric map of Lydonia Canyon, U.S. Atlantic 

Outer Continental Shelf: U.S. Geological Survey Miscellaneous Field Studies Map MF-1710, scale 1:50,000. 

Butman, Bradford, Noble, M.A., Beardsley, R.C., and Chapman, 

D.C., 1983, An upper bound for the tidally rectified current 

at one location on the southern flank of Georges Bank: 

Journal of Physical Oceanography, v. 13, no. 8, 

p. 1452-1460. 

Butman, Bradford, Noble, M.A., and Folger, D.W., 1979, 

Long-term observations of bottom current and bottom 

sediment movement on the Mid-Atlantic continental shelf: 

Journal of Geophysical Research, v. 84, no. C3, 

p. 1187-1205. 

Csanady, G.T., Churchill, J.H., and Butman, Bradford, 1988, 

Near-bottom currents over the continental slope in the 

Mid-Atlantic Bight: Continental Shelf Research, v. 8, 

p. 653-671. 

Moody, J.A., Butman, Bradford, Beardsley, R.C., Brown, W.S., 

Daifuku, Peter, Irish, J.D., Mayer, D.A., Mofjeld, H.O., 

Petrie, Brian, Ramp, Steven, Smith, Peter, and Wright, 

W.R., 1984, Atlas of tidal elevation and current observations on the northeast American continental shelf and 

slope: U.S. Geological Survey Bulletin 1611, 122 p. 

Noble, M.A., Butman, Bradford, and Williams, E., 1983, On the 

longshelf structure and dynamics of subtidal currents on the 

eastern United States continental shelf: Journal of Physical 

Oceanography, v. 13, p. 2125-2147. 

Noble, M.A., Butman, Bradford, and Wimbush, M., 1985, The 

temporal and frequency structure of wind-current coupling 

on Georges Bank: Journal of Physical Oceanography, v. 

15, p. 604-620. 

Strahle, William, and Butman, Bradford, 1985, Modification of 

EG&G vector averaging current meter to record light 

transmission and water conductivity: U.S. Geological Survey Open-File Report 85-106, 22 p. 

Twichell, D.C., 1983a, Bedform distribution and sand transport 

on Georges Bank, United States Atlantic continental shelf: 

Sedimentology, v. 30, p. 695-710. 

---1983b, Geology of the head of Lydonia Canyon, U.S. 

Atlantic Outer Continental Shelf: Marine Geology, v. 54, 

no. 1-2, p. 91-108. 

Twichell, D.C., Butman, Bradford, and Lewis, R.S., 1987, 

Shallow structure, surficial geology, and the processes 

currently shaping the Bank, chap. 4, in Backus, R.H., ed., 

Georges Bank: Cambridge, Mass., M.I.T. Press. p. 31-37. 

Twichell, D.C., McClennen, C.E., and Butman, Bradford, 1981, 

Morphology and processes associated with the accumulation of the fine-grained sediment deposit on the southern 

New England shelf: Journal of Sedimentary Petrology, 

v. 51, no. 1, p. 269-280. 

Uchupi, Elazar, 1968, Atlantic continental shelf and slope of the 

United States-Physiography: U.S. Geological Survey Professional Paper 529-C, 30 p. 

Toward a Capability for Predicting Transport of Sediments 101 

24. Characteristics of Coal-Mine Wastes for 

Rehabilitation Work 

By R.C. Severson 

Many of the soil-element availability techniques commonly used in agronomy are being applied to minerehabilitation sites because of the need for monitoring metal 

levels in both plants and mine soils. This application was 

prompted by mandates from reclamation guidelines. In 

actuality, these tests have proven to be most reliable for 

establishing deficiency levels of trace elements in soils. 

Using the same tests to define toxicity or maximum permissible levels (MPL) has caused much confusion for both 

regulators and mine operators. Plant species used in minedland rehabilitation probably do not respond the same as 

agricultural plants in their uptake or exclusion of trace 

elements. Because recommendations differ for each agricultural crop, similar allowances should be made for each 

rehabilitation species. If doubts exist concerning the stated 

permissible levels and how they should be determined, then 

inequitable enforcement of regulations may result when 

enforcement is based on interpretations of these soil tests for 

different rehabilitation plant species. 

To test the usefulness of diethylenetriamine pentaacetic acid (DTPA) a predictor of soil-plant relations, we 

sampled 11 areas (fig. 24.1) that varied greatly in edaphic, 

geological, geochemical, and climatic conditions and in 

mining and rehabilitation practices. 

In the Western United States, DTPA-extractable 

metal levels in soil and overburden have been used as 

indicators of potentially toxic conditions for plant establishment and growth on rehabilitated land. Proposed upper 

limits, or permissible levels, and actual concentrations in 

both natural soils and mine soils in the northern Great Plains 

are given in Severson and Gough (1981, 1983). These 

studies indicate that DTPA-extraction measures under field 

conditions are inadequate for relating available metals in 

mine soils to metal uptake by rehabilitation plant species. 

Extraction measures do, however, provide data useful in 

defining provisional plant-physiological-tolerance ranges, 

while further basic research is conducted on the mine 

soil-plant system. 

Proposed MPL' s of trace elements were compared to 

the measured DTPA-extractable concentrations in cover 

soil, spoil, and A and C horizons of natural soil. In all these 

MONTANA 

450 '--- i WYOMING--

I 

i 

I 

I 

I -1 

I 

l_ 

---TNo~~ I 

I 

I Fort Union Region i 2e 

: 3e 

Coal Mines Studied Within 

Coal Resource Regions 

1-Velva 

2-South Beulah 

3-Huskv 

4 Big Sky 

5-Absaloka 

6-Decker West 

7-Dave Johnston 

8-Seminoe II 

9-Jim Bridger 

10-Seneca II 

11-Energy Mines 

Figure 24.1 General locations of the coal surface mines 

sampled in the Western United States. From Severson and 

Gough (1984.) 

materials, the maximum levels of copper, manganese, lead, 

and zinc were well below the proposed MPL. For cadmium 

and nickel, the maximum amounts measured in cover soil 

and spoil at several mines, as well as 95 percent in A and C 

horizons of native soil, exceeded the proposed MPL. At 

only one mine was iron in spoil greater than the proposed 

MPL, but iron in cover soil and spoil at several mines was 

greater than that expected in natural soils. 

Mine soils represent a youthful stage of soil development, and the rapid changes in their chemical equilibrium 

should be expected. The sedimentary rocks that were 

previously confined to a presumed reducing and biologically inactive zone are exposed by mining to an oxidizing 

environment that is biologically active. 

Many soil extractants have been proposed as being 

universal for both native and disturbed soils but were 

Characteristics of Coal-Mine Wastes for Rehabilitation Work 1 03 
subsequently abandoned. The concepts of intensity and 

capacity factors may be good starting points for the development of soil extracts for use on overburden material and 

soils of rehabilitated strip mines. How these factors might 

be applied to the development of new soil extracts is 

summarized here from a written communication by G. 

Sposito (University of California-Riverside, 1982). Potential bioavailability (capacity factor) of trace elements in 

rehabilitated mine soils can be estimated from extracts by 

using chelates such as ethylenediaminetetraacetic acid 

(EDT A) or DTP A only after the action of these chelates on 

minerals has been established. In general, chelate extractability implies susceptibility to weathering over time, 

whereas inorganic acid extractability implies resistance to 

weathering over time. Actual bioavailability (intensity factor) of trace elements in rehabilitated mine soil can be 

estimated from a water-saturation extract. This estimate 

might best be done by leaching mine soils with natural 

water (for example, precipitation) and determining the 

solubility of the solid phase of the soil during the leaching 

process. Such data would be useful in describing the actual 

bioavailability over short time periods. In addition, the 

leachate composition would be used to assess trace-element 

mobility. 

REFERENCES CITED 

Severson, R.C., and Gough, L.P., 1981, Chemical character of 

mine soils at one Alaskan and twelve western conterminous 

United States coal-stripmines: U.S. Geological Survey 

Open-File Report 81-243, 82 p. 

---1983, Rehabilitation materials from surface-coal mines in 

Western U.S.A., pt. I, Chemical characteristics of spoil 

and replaced cover-soil: Reclamation and Revegetation 

Research, v. 2, p. 83-102. 

104 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
25. The Role of Coal Characterization 

in the Control of Acid Precipitation 

By jack H. Medlin and Frederick 0. Simon 

INTRODUCTION 

Recent studies by the Committee on Atmospheric 

Transport and Chemical Transformation in Acid Precipitation (1983) and the General Accounting Office (1981) have 

concluded that atmospheric acid precipitation constitutes a 

hazard to man's environment. They further suggest that 

emissions from coal-fired powerplants may contribute significant amounts of acid-causing elements to the atmosphere. Their conclusions indicate that much research is 

necessary before the legislative process forces changes in 

operating procedures that may be excessively costly or 

ineffective. There is much uncertainty among policymakers, scientists, economists, and executives as to how to 

mitigate the effects of acid rain and to control the amount of 

sulfur emitted from coal-fired powerplants. One recommended solution to the problem includes tightening the 

standards of the Clean-Air Act to reduce sulfur dioxide 

emissions, which would be accomplished by the installation 

of scrubbers on existing and future powerplants. This 

approach may be sound from scientific and engineering 

viewpoints, but for older powerplants, it may be unsound 

from an economic viewpoint. The ongoing debate in various trade, scientific, and technical publications leads one to 

conclude that there is wide disagreement on the approaches 

to the solution of the problem. We believe that the application of scientific and technical methods, heretofore not 

widely considered, may alleviate the need for intensive 

application of scrubber technology and may help to obviate 

the need for scrubbers in individual cases. Although these 

approaches have not been entirely overlooked, they have 

not been emphasized to the extent that we feel is necessary 

to contribute to solutions of the acid-precipitation problem 

and to help with the continued or expanded use of coal. 

PAST AND CURRENT STUDIES 

Before 1984, most studies emphasized environmental 

monitoring as a means of determining whether a problem 

existed. Atmospheric distribution was studied to delineate 

possible sources of acid rain and to track its geographic 

progress; physiochemical pathways were investigated to 

ascertain reaction mechanisms; and observations were made 

of the effect of acid precipitation on various biologic, 

hydrologic, and geologic systems (National Acid Precipitation Assessment Program, 1983). These approaches address 

only half of the system with which we are dealing, and 

indeed scientists modeling the problem have indicated that 

valid data are insufficient to complete existing models. Past 

and present studies have not adequately emphasized that 

acid precipitation is affected by a system whose spectrum 

covers a span from in-ground coal resources to the acidification of streams, lakes, soils, and so on, and its subsequent 

effects on the ecosystem. To make sound scientific judgments or to provide sound technical options for policymakers requires that the entire spectrum be examined in detail, 

that systematic efforts to deal with the acid rain problem be 

made from a credible and reliable knowledge base, and that 

the results be balanced, equitable, and achievable. 

A large part of the know ledge base being used today 

is founded upon inadequate characterization of our coal 

resources. Many assessments of quality and quantity are 50 

or more years old and reflect not only outmoded techniques 

and technology but also mined-out, exhausted, and abandoned mining areas. Consequently, many of the oftenquoted conclusions concerning sulfur content and regulations are based on coal analyses of questionable merit. 

Current areas of research in the acid-precipitation 

problem are indicated in the right half of figure 25.1, which 

is redrawn from a sketch that appeared in a special report of 

the Electric Power Research Institute (Moore, 1983) 

devoted to acid-rain research. Research efforts in these 

areas include identification of point sources, monitoring the 

problem, impact on ecosystems, and so on. The starting 

points for many existing studies are the powerplants where 

emissions of potential pollutants originate and whose emissions contribute to various atmospheric, physiochemical, 

biological, and hydrologic reactions and interactions. 

In our view, these areas constitute only half of the 

system. In the left half of figure 25.1, we added three 

additional areas that we believe must be considered to 

The Role of Coal Characterization in the Control of Acid Precipitation 1 05 
.-.......... 

Figure 25.1. The link between resource identification, mining, and coal preparation and pollution emissions and the fate 

of acidic compounds in the atmosphere. From Moore, 1983. 

effectively attack the acid-precipitation problem. The first 

area is identification and delineation of the coal resource; 

the second is the extraction or mining stage; and the third is 

the coal preparation stage. These areas represent stages of a 

cycle in which various options can be identified at each 

stage, tradeoffs made, and decisions implemented to minimize the amount of acid precipitation progenitors that will 

be emitted into the atmosphere. The consideration of these 

three additional areas should lead to more sound scientific 

and economic options concerning the mitigation and regulation of the emission of sulfur dioxide and other deleterious 

substances. 

We will focus on these three areas and discuss in 

detail the role that coal characterization can play in addressing the acid precipitation problem. However, we first must 

define coal characterization or coal quality. 

COAL QUALITY 

An all-encompassing definition of coal quality is 

probably impossible to devise because quality requirements 

differ according to the end use of the coal. Utilities require 

coal that has different properties from the steel industry, 

whose requirements may substantially differ from those 

users who gasify or liquefy or use coal as a chemical 

feedstock (fig. 25.2). Each powerplant is uniquely designed 

and built for coal that has closely defined physical and 

chemical properties. Thus, each powerplant has different 

quality requirements. In times past, powerplant operators 

were interested only in calorific value and ash content. 

Later, with some encouragement from the Government, 

sulfur was included. Economics, burning characteristics of 

coal, corrosion and fouling of boiler tubes, and other 

concerns have expanded the list of tests in which the 

powerplant operator is interested. Recently, they also began 

to consider ash fusion temperatures; major, minor, and 

trace-element composition; and hardgrove grindability 

index. Today, powerplant operators are concerned with all 

of the characteristics of coal quality. 

The data used to implement existing or proposed 

regulations are based on various sources. Careful evaluation 

of these sources shows the data to be incomplete, not 

comprehensive, not comparable, and inadequately verified. 

For example, much existing sulfur data cannot be related 

directly to in-ground resources. Analyses were done on a 

mixture of run-of-mine, grab, delivery, or otherwise unrepresentative types and generally were inadequately documented. Chemical analyses were made by a variety of 

techniques, were determined by old and new methods, and 

were derived from many laboratories using different standards and techniques. The results, therefore, are not representative of the coal bed or coal-bearing sequence from 

which they- are purported to come. Credible, reproducible 

data are needed for all coal beds and coal-bearing regions of 

the United States; samples must be point located and 

106 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
PORE VOL., INTERNAL 

SURFACE AREA 

SYNFUELS 

VITRINITE, EXINITE, 

INERTINITE 

TRACE ELEMENTS 

STEEL INDUSTRY 

BTU, ASH, S 

MOISTURE, VM, 

ASH FUSION 

N, Na, Cl, 

HARDGROVE INDEX 

UTILITIES 

S, N, C, As, Se, Hg, 

Pb, Cd, 

F, V, Cr, Ni, Cu, Zn 

Be, Tl, U, Th, Sn, 

ENVIRONMENTAL 

Figure 25.2. Coal-quality parameters important in coal utilization. Less common abbreviations used in this figure are VM 

(volatile matter), FSJ (free swelling index), and pore vol. (pore volume). 

correlated, and sampling procedures must be standardized. 

Limited data bases exist on the national and State levels, 

and industry possesses (confidential) data for tracts in which 

they have an interest. The most extensive of these data 

bases is resident in the U.S. Geological Survey (USGS) 

(table 25.1). It contains data on 128 parameters for more 

than 6,200 correlated coal samples-but most of those 

samples are from only a few beds, and we have a long way 

to go to obtain adequate coverage for the entire United 

States. In fact, this data base has data (one or more samples 

per coal bed per county) for only one-third of the coal 

resources in the U.S. Bureau of Mines' demonstrated 

coal-reserve base (U.S. Bureau of Mines, 1974). 

Analysis of coal samples should include not only 

those determinations that are economically or use related 

but also the entire list of major, minor, and trace elements. 

One might ask why we should be concerned with trace 

levels of contaminants that most people have never heard 

of. The answer is that these elements are being remobilized 

by the mining and combustion processes and consequently 

are made available to the environment. Table 25.2 lists the 

amounts of selected elements that are mobilized as a result 

of the annual coal production for a typical 1 ,000-megawatt 

(MW) powerplant for the United States for the years 1978 

and 2000 and for the world for the years 1978, 2000, and 

1979-2000. Although the elements are present in coal in 

trace amounts, the large amount of coal being burned causes 

the potential for contamination from trace toxic elements to 

be great. If scrubbers are used, a proportion of the contaminants in table 25.2 will end up in the scrubber sludge, 

causing disposal and potential ground-water pollution problems that should not be ignored (approximately 50 percent 

of the U.S. population depends on ground water as a source 

of drinking water). The fate and consequences of the 

availability to the environment of volatile constituents such 

as arsenic, antimony, selenium, fluorine, and mercury are 

less known and less understood, but they are much more 

toxic than sulfur or nitrogen. Almost 200 tons of these five 

elements will be emitted annually from a typical1 ,000-MW 

powerplant. These amounts can be altered by one to two 

orders of magnitude (either up or down) by selecting the 

appropriate coal feedstock. 

Coal is a heterogeneous substance that contains both 

organic and inorganic elements and compounds. The two 

elements that most directly impact the acid-precipitation 

problem are sulfur and nitrogen; they also seem to be the 

two most frequently cited variables of concern in the 

acid-precipitation debate. However, other contaminants can 

The Role of Coal Characterization in the Control of Acid Precipitation 1 07 
Table 25.1. Data items for the U.S. Geological Survey National Coal Resources Data System's USCHEM data base 

1. State 44. BMASH (750 °C) 87. Ge- germanium 

2. County 45. Carbon 88. Hf- hafnium 

3. Latitude 46. Oxygen 89. Hg- mercury 

4. N/S 47. Hydrogen 90. Ho- holmium 

5. Longitude 48. Nitrogen 91. In- indium 

6. E/W 49. Sulfur (total) 92. Ir- iridium 

7. AAPG1 province 50. Sulfur (sulfate) 93. La - lanthanum 

8. Coal province 51. Sulfur (pyritic) 94. Li- lithium 

9. Region 52. Sulfur (organic) 95. Lu - lutetium 

10. Field 53. Air-dried loss 96. Mn - manganese 

11. District 54. USGSASH (525 °C) 97. Mo - molybdenum 

12. Formation 55. Si02 

13. Group 56. Al20 3 

14. Bed 57. CaO 

15. Member 58. MgO 

16. Zone 59. Na20 

17. Depth 60. K20 

18. Sample thickness 61. Fe20 3 

19. System 62. MnO 

20. Series 63. Ti02 

21. Location name 64. P20 5 

22. Quadrangle 65. so3 

23. Collector 66. Ag - silver 

24. Field ID No. 67. As - arsenic 

25. Date 68. Au- gold 

26. Estimated rank 69. B- boron 

27. Rank (class; calc'd.) 70. Ba - barium 

28. Rank (group; calc'd.) 71. Be - beryllium 

29. ID (alpha) 72. Bi- bismuth 

30. ID (numeric) 73. Br- bromine 

31. Labcode 74. Cd- cadmium 

32. Sample type 75. Ce- cerium 

33. Analysis type 76. Cl - chlorine 

34. Values represent 77. Co- cobalt 

35. NCRDS check 78. Cr - chromium 

36. Calorific value 79. Cs- cesium 

37. Ash deformation temp. 80. Cu- copper 

38. Ash softening temp. 81. Dy - dysprosium 

39. Ash fluidization temp. 82. Er- erbium 

40. Free swelling index 83. Eu - europium 

41. Moisture 84. F- fluorine 

42. Volatile matter 85. Ga- gallium 

43. Fixed carbon 86. Gd - gadolinum 

1 American Association of Petroleum Geologists. 

act synergistically to either accelerate or retard reactions 

involving these variables, but these constituents have not 

been extensively studied. More studies of these trace 

contaminants are needed because we are dealing with a 

multivariant system. 

COAL-RESOURCE IDENTIFICATION AND 

DELINEATION 

Figure 25.3 shows the coal basins of the United 

States. The first stage of a comprehensive program to abate 

acid precipitation is the identification and delineation of the 

remaining, in-ground coal resources of North America. It is 

98. Nb- niobium 

99. Nd - neodymium 

100. Ni- nickel 

101. Os- osmium 

102. Pb- lead 

103. Pd - palladium 

104. Pr- praseodymium 

105. Pt - platinum 

106. Rb - rubidium 

107. Re- rhenium 

108. Rh- rhodium 

109. Ru - ruthenium 

110. Sb - antimony 

111. Sc - scandium 

112. Se - selenium 

113. Sm - samarium 

114. Sn- tin 

115. Sr - strontium 

116. Ta - tantalum 

117. Tb- terbium 

118. Te - tellurium 

119. Th- thorium 

120. Tl - thallium 

121. Tm- thulium 

122. U- uranium 

123. V- vanadium 

124. W- tungsten 

125. Y- yttrium 

126. Yb - ytterbium 

127. Zn- zinc 

128. Zr- zirconium 

common knowledge that almost 4 trillion tons of coal 

resources have been identified or speculated to occur in the 

United States (Averitt, 1975). Moreover, the U.S. Bureau 

of Mines (1974) and the U.S. Department of Energy (1981) 

have concluded that 438 to 474 billion tons of these 

resources are economically recoverable by existing technology. The quantity is not the most important factor, but the 

magnitude of the numbers causes much misunderstanding 

among decisionmakers and even among scientists and 

technical people studying U.S. coal. 

The most important aspects in the discussion of coal 

resources, once it is concluded that there is a lot of coal, are 

the quality of that coal, the distribution and occurrence of 

the high-quality coal, and the methods or techniques that 

108 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Table 25.2. Quantities of trace elements mobilized as a result of coal production 

[Modified from Zubovic and others, 1979. Data are in tons; MW, megawatts] 

Typical 

Element 1,000-MW 

plant (annual 

production) 

Sulfur ................................. 30,500 

Arsenic ................................ 13.7 

Beryllium .............................. 3.8 

Cadmium .............................. 0.4 

Cobalt ................................. 9.4 

Chromium ............................. 25.3 

Copper ................................ 32.3 

Fluorine ............................... 174.2 

Mercury ............................... 0.24 

Lithium ................................ 22.4 

Manganese ............................. 66.3 

Molybdenum ........................... 5.0 

Nickel ................................. 19.5 

Lead .................................. 19.1 

Antimony .............................. 1.6 

Selenium .............................. 4.6 

Uranium ............................... 3.5 

Vanadium ............................. 40.6 

Zinc ................................... 37.7 

exist to improve the quality of the coal to make it meet 

usage and environmental requirements. The notion of the 

quantity of U.S. coal is very much like arguments over 

clean air. It is not the quantity of air we are immediately 

concerned about (it being assumed that there is a lot of it), 

but the quality of that air, the concentration and distribution 

of its pollutants, and how to maintain air quality without 

disrupting the industrial base of the nation that are of 

interest. Figure 25.4 illustrates the present state of our 

resource knowledge when considering coal-quality parameters. Each vertical bar represents a concentration bracket 

for sulfur, and the height of the bar represents the tonnage 

of coal having the specified sulfur content in the U.S. 

Bureau of Mines demonstrated reserve base. Although 

differences in the concentration bands exist among basins, 

the ''unknown" bar is uniformly large for all basins. 

At present, our knowledge and understanding of the 

sulfur and nitrogen concentration and distribution in U.S. 

coals are better than for any other contaminant, and yet they 

are vague and very general if one considers the in-ground 

coal resources. For example, one frequently hears such 

statements as, "Appalachian coal is medium sulfur"; "Midcontinent coal is high sulfur"; "Western coal is low sulfur.'' 

These gross generalizations are misleading and oversimplified because we know that, in parts of the midcontinent and Appalachian coal fields, a potential exists for large 

quantities of low-sulfur, high-quality coal. It also is generally known, but little publicized, that large areas within 

these coal basins are unexplored and little quality characUnited States World 

1978 2000 1978 2000 1979-2000 

7X 106 19X 106 41 X 106 105X 106 1700X106 

3,300 8,400 19,000 47,000 770,000 

910 2,300 5,100 13,000 210,000 

91 230 510 1,300 21,000 

2.270 5,800 13,000 33,000 530,000 

6,110 15,000 34,000 87,000 1,400,000 

7,800 20,000 43,000 110,000 1,800,000 

42,000 110,000 230,000 590,000 9,700,000 

59 150 328 843 14,000 

5,400 14,000 30,000 77,000 1,300,000 

16,000 41,000 91,000 230,000 3,800,000 

1,200 3,000 6,500 17,000 270,000 

4,700 12,000 26,600 68,000 1,100,000 

4,600 12,000 25,000 65,000 1,100,000 

380 950 2,100 5,400 88,000 

1,100 2,800 6,200 16,000 250,000 

850 2,100 4,700 12,000 200,000 

9,800 25,000 54,000 140,000 2,300,000 

9,100 23,000 51,000 130,000 2,100,000 

terization exists for them. In the eastern U.S. coal fields, 

unexplored areas are located away from coal-field margins. 

Figure 25.5 outlines the Pittsburgh coal bed; the dots mark 

the locations of samples for which analytical data are stored 

in the USGS USCHEM data base. The paucity of data in the 

center of the coal field is apparent. What is needed is to 

identify, delineate, and characterize the coal in these 

unexplored areas. Moreover, the Pittsburgh coal bed is one 

of the best characterized coal beds in the United States; for 

most other coal beds, the distribution of analyses is worse 

than that depicted in figure 25. 5. There also is a need to 

characterize coal beds in areas being mined so that selected 

mining and blending can be used to reduce sulfur and 

nitrogen contents to acceptable levels. 

Characterization of in-ground resources allows development of viable options concerning feedstock specifications and sources; it also allows fundamental decisions to be 

made concerning extraction methods and whether to clean, 

blend, crush, or size the coal before combustion in powerplants. This kind of knowledge can lead to the development 

of models that will allow prediction of the potential so2 

emissions for a region, as well as for a single power facility, 

and for the short-, medium-, and long-term future. 

SELECTIVE MINING AND BENEFICIATION 

The second stage of a comprehensive program for the 

abatement of acid precipitation involves improvements in 

the extraction and beneficiation of coal. In-ground coalThe Role of Coal Characterization in the Control of Acid Precipitation 1 09 
Anthracite and semianthracite 

Low-volatile bituminous coal 

Medium- and high-volatile 

bituminous coal 

Subbituminous coal 

Ugnite 

Figure 25.3. Coal basins of the continental United States. From Garbini and Schweinfurth (1986). 

resource characterization will provide options and allow a 

greater range of decisions concerning selective mining of 

several coal beds or blending of coal from one or more beds 

within the same mine or from several mines within the coal 

field. Regional knowledge and site-specific data can frequently allow, through blending, an opportunity to reduce 

the sulfur and nitrogen contents to acceptable levels before 

combustion without cleaning the coal or scrubbing the 

emissions. This is especially beneficial for older powerplants whose economic situation will not justify the retrofit 

installation of scrubbers. If the adaptation of low-sulfur and 

low-nitrogen coal sources can be gradual, the disruption of 

the mining industry will be minimal. 

Figure 25.6 illustrates how selective mining can help. 

This actual example shows a mine in an eastern coal field 

containing bed A and three benches of bed B; the sulfur and 

ash contents are shown. Within 200 feet of stratigraphic 

section and 1 mile distance, sulfur content ranges from 1.52 

to 15.0 percent, and ash content ranges from 9.09 to 18.29 

percent. 

110 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
POWDER RIVER BASIN 

1-

"' 

0 

z 10 

~ ~ ::~ 1-

a:• ~ ~"'! 0 0 6 ~"'! ; 

.,_ 

:r . ~ ~~~ 4 "' ~A~ 

z ~ , ; 

~ "~ .. 0 ... .. p ~ ~ .. , .. .. ... ., "' "' "' p 

,. c. ~ 

~ ; ; , ~ ' \ ·~ "' ; ; ' p 

·~ ~ ' , "' ; 0 p ; i. 

.,. CONCENTRATION BAND ('I.) 

NORTHERN APPALACHIAN 

BASIN 

~ 

~ p 

... ., ' ~ '! p 

CONCENTRATION BAND ('It) 

WESTERN INTERIOR SOUTHERN APPALACHIAN 

BASIN 

CENTRAL APPALACHIAN 

"' 10 z 

0 

1-

1- ~ 

~ e 6 

:r • 

"'- 4 z 

2 

.... 

.... 

,. 

·., ; 

"', ' ; 

; ·~ 

; ~ ~ 

·~ p 

, ' ' p "' ; 

"' z 30 0 

1- 25 

0 

~ 1-.,_ ~ ; oi. 

~ ; "', ' 

' ·~ 

"' ' ·~ ' 

~ .,. 

~ ~ \ p 

' "' "' ; 0 

' i. 

.,. 

"' z 

0 

IIa: 

0 

:r 

"' z 

0 

::; 

.... 

i 

14 

10 

·- ... ... ~ c. ·"', ' ' , 1;c ' ' .... p 

' ' "' .,_oi. .... " "' p ' ' .,. CONCENTRATION BAND (~) CONCENTRATION BAND (%) CONCENTRATION BAND (!.) 

Figure 25.4. Total sulfur plotted against demonstrated reserve base of coal in the United States. Sulfur data are divided 

into seven bands and related to reserve tonnage. 

PREPARATION AND BENEFICIATION 

The third stage in the proposed program, coal preparation , has been a standard procedure in the coal industry 

for many years. Upgrading coal quality with selective 

beneficiation methods helps to meet the specifications of the 

end user. Most of these specifications are limited to higher 

calorific value and lower sulfur and ash contents than 

naturally occur in a coal bed; these objectives are accomplished by using heavy liquid media , crushing, sizing, 

screening, and blending (fig. 25.7). The efficiency of the 

entire coal-preparation process is predicated on the quality 

of the in-ground coal resources. Changes in the physical and 

chemical properties of the feedstock change that efficiency. 

Furthermore, it should be emphasized that most cleaning 

processes are not designed to deal with organically bound 

elements. Virtually all of the nitrogen and approximately 

half of the sulfur in coal are organically bound . Chemical 

techniques are more successful in removing organic sulfur, 

but these have seen only limited experimental application 

because of the high cost. In addition, finely divided 

minerals that are intimately mixed with organic matter (the 

source of inherent ash) cannot be removed by normal 

cleaning techniques; fine grinding methods could provide a 

technical breakthrough. More than 150 minerals from coal 

have been identified (Gluskoter, 1978; Finkelman, 1980; 

Gluskoter and others, 1981). Some of these are listed in 

table 25.3. 

Coal is an inhomogeneous material that changes 

laterally (regionally) and vertically (stratigraphically). As a 

result, coal-resource characterization is needed to anticipate 

the natural changes in coal quality and to estimate the rate 

of change. In addition, basic information on coal structure 

and the modes of occurrence of trace contaminants can 

contribute to the design of cleaning processes to eliminate 

much of the contamination from toxic elements. One of the 

ironies of many coal characterizaton studies is that they 

were performed on coal that had already been mined. Many 

environmental regulations and mitigation measures are 

based solely on data for coal that is no longer there. 

We have shown that, with increased emphasis on coal 

cleaning and the development of new and improved cleaning methods, sulfur, nitrogen, and other contaminant concentrations can be reduced. This reduction will lead to a 

cleaner fuel being introduced into the powerplants and less 

resultant contamination of the atmosphere. We also have 

shown that, by carefully characterizing the resource, by 

taking greater care in mining, and by cleaning and blending 

coals, the need for scrubbers will be reduced considerably 

or be made unnecessary. 

The Role of Coal Characterization in the Control of Acid Precipitation 111 
• 

Pennsylvania 

• 

Ohio 

West Virginia 

Virginia 

Figure 25.5. Outline of the Pittsburgh coal bed showing sample locations (black circles) for which analytical data are 

stored in the U.S. Geological Survey's USCHEM data base. 

CURRENT SULFUR EMISSION STANDARDS 

As of 1984, the Environmental Protection Agency 

(EPA) standard allowed the emission of 1.2 pounds of S02 

per million Btu. In 1980, this standard permitted an 

estimated emission of 15 ,908,000 tons of S02 (Argonne 

National Laboratory, 1983). Bills introduced in the U.S. 

Congress in 1981 and 1982 require future total S02 emissions to be reduced by 6.5 to 13 million tons per year or 0.6 

pounds of S02 per million Btu (Armbruster and others, 

1983). Armbruster and others (1983) and Brady (1983) 

estimate that the cost of meeting these standards ranges 

from $3 billion to $12 billion annually for a reduction of 8 

million to 10 million tons of S02 per year. These estimates 

are based on several assumptions, but one that bears some 

discussion is a commonly held misconception that a switch 

to low-sulfur western coal will solve the problem. One 

needs to examine this option with some care; most lowsulfur western coal also is much lower in Btu's than 

midwestern and eastern U.S. coal. Figure 25.8 shows that, 

when considered on a Btu basis, coal having equal or lower 

sulfur and ash contents can be found in the East. Careful 

and systematic characterization of all U.S. coal resources 

may reveal more low-sulfur, high-Btu coal that can directly 

meet the S02 reductions or that can be cleaned or blended 

to meet proposed reduced standards. 

At present, it is difficult to obtain a specific estimate 

of the magnitude of the acid-precipitation problem because 

our data base on sulfur and nitrogen contents in coal allows 

us to estimate only on large regional areas, and, as we have 

demonstrated , most of these estimates are for coal that has 

already been mined or that is being mined. There are no 

credible and reliable data on the sulfur and nitrogen contents 

of coal that will be mined in the long term because little 

exploration or analysis has been undertaken in these areas. 

EFFECT OF CHANGES IN THE S02 EMISSION 

STANDARD 

Recent studies by the Kentucky Geological Survey 

(Cobb and others, 1982, 1983) estimated the impact of 

reducing the present 1.2 pounds S02 per million Btu 

standard on Kentucky's coal resources (see fig. 25.9). By 

using the EPA standards for both operating and new 

112 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Figure 25.6. Example of variability of sulfur and ash (in percent) within a mine in an eastern coal field. (Courtesy of P.C. 

Lyons, U.S. Geological Survey.) 

powerplants (1.2 and 0.6 pound S02 per million Btu, 

respectively) and a probability model, Cobb and others 

predicted that approximately 50 percent of the coal 

resources in eastern Kentucky is in compliance at the 

1.2-pound standard, whereas only I percent of the resources 

is estimated by the model to be in compliance at the 

0.6-pound standard. Their studies show that lowering the 

standard will bring hardship on the coal industry of the 

leading coal-producing State in the Nation. A larger and 

more detailed data base may identify lower sulfur resources 

and, combined with cleaning and blending, may aid in 

greatly reducing the so2 levels, although it is unlikely that 

the reductions will be sufficient to satisfy the 0.6-pound 

standard. 

COAL-QUALITY MODELS AND REGULATIONS 

Modeling coal quality can greatly enhance our ability 

to predict the quantities of low-, medium-, and high-sulfur 

coal still available at local, regional, and national scales. 

The physical, biological, and chemical conditions of the 

ancient peat swamp, and their interaction with the indigenous plant materials, led to the formation of specific types 

of peat and hence to specific types of coal. Environmental 

influences such as the proximity to marine conditions 

(sources of sulfur), the types of plants contributing to the 

swamp, and geochemical influences such as acidity, redox 

potential, and the type of sulfur compounds present affect 

the characteristics of the peat and the amount of sulfur that 

ends up in the coal. For example, Dorofeev (1974) concluded that typical sulfur contents of Carboniferous coals of 

the Donetz in the U.S.S.R. varied according to their 

environment of deposition (table 25.4). 

The variations in coal properties affected by the 

depositional environment may have been local or widespread. Many of the factors influencing the quality of coal 

have left their fingerprints in the geologic record and, with 

the proper geologic controls, can be used to develop models 

for the prediction of coal quality in areas where analytical 

data are lacking. The danger lies in making broad generalizations without adequate models or supporting evidence. 

The Role of Coal Characterization in the Control of Acid Precipitation 113 
Figure 25.7. Standard procedures in coal preparation . 

CONCLUSIONS 

Regulations can be based on coal-quality models if 

the models are based on sound data and sound scientific 

judgment and if the models are applied properly . Models 

based on inadequate or inaccurate data can lead only to 

unsound regulations at best and, at worst, will produce 

extreme hardships on a large portion of society. 

COAL PILE 

In conclusion, the Nation needs a comprehensive 

program to provide a balance among coal characterization, 

selective mining, coal cleaning, scrubbers, and the use of 

new and existing powerplants. It is time to stop dealing with 

only one-half of the spectrum; it is time to gather some very 

basic data that will lead to the development of more options 

(other than scrubbers) to address the acid-rain problem. 

114 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Table 25.3. Minerals known to occur naturally in coal 

[From Gluskoter and others, 1981; Mineral formulas according to Bates and Jackson, 1987] 

Mineral Formula 

Clay minerals 

Montmorillonite .......... Al2Si4 0 10(0H)zH20 

Illite-sericite. . . . . . . . . . . . . . KAlz(AlSi30 10)(0H)z 

Kaolinite................. Al4Si4 0 10(0H)4 

Halloysite ................ Al2Si 20 10(0H)4H20 

Chlorite (prochlorite,. . . . . . Mg6A1Si30 10(0H)8 

penninite) 

Mixed-layer clay minerals . 

Sulfide minerals 

Pyrite . . . . . . . . . . . . . . . . . . . . FeS2 

Marcasite . . . . . . . . . . . . . . . . FeS2 

Sphalerite . . . . . . . . . . . . . . . . ZnS 

Galena ................... PbS 

Chalcopyrite. . . . . . . . . . . . . . CuFeS2 

Pyrrhotite . . . . . . . . . . . . . . . . Fe 1_xS 

Arsenopyrite. . . . . . . . . . . . . . FeAsS 

Millerite . . . . . . . . . . . . . . . . . NiS 

Carbonate minerals 

Calcite . . . . . . . . . . . . . . . . . . . CaC03 

Dolomite. . . . . . . . . . . . . . . . . CaMg(C03)z 

Siderite . . . . . . . . . . . . . . . . . . FeC03 

Ankerite ................. Ca(Fe,Mg,Mn)(C03)z 

Witherite ................. " BaC03 

Sulfate Minerals 

Barite .................... BaS04 

Gypsum .................. CaS04·2H20 

Anhydrite ................ CaS04 

Bassanite. . . . . . . . . . . . . . . . . CaS04·1/2H20 

Jarosite .................. KFeiS04)z(OH) 6 

Szomolnokite. . . . . . . . . . . . . FeS04 • H20 

Rozenite ................. FeS04·4H20 

Melanterite ............... FeS04·7H20 

Coquimbite. . . . . . . . . . . . . . . Fe2 (S04 h·9H20 

Roemerite ................ Fe +2Fe +3(S04 ) 4·14H20 

Mirabilite . . . . . . . . . . . . . . . . Na2S04·10H20 

Kieserite . . . . . . . . . . . . . . . . . MgS04 • H20 

Sideronatrite.............. Na2Fe +3(S04 )z(OH)· 3H2 0 

Mineral 

Chloride minerals 

Halite. . . . . . . . . . . . . . . . . . . . NaCl 

Sylvite . . . . . . . . . . . . . . . . . . . KCl 

Formula 

Bischofite ................ MgC12·6H20 

Silicate minerals 

Quartz . . . . . . . . . . . . . . . . . . . Si02 

Biotite ................... K(Mg,Fe +2h(Al,Fe +3)Si30 10 

(OH)z 

Zircon ................... ZrSi04 

Tourmaline. . . . . . . . . . . . . . . (Na,Ca)(Mg,Fe +Z ,Fe +3 ,Al,Lih 

Al6 (B03hSi60 18(0H)4 

Gamet ................... (Ca,Mg,Fe+2 ,Mn+2h(Al,Fe+3 , 

Mn +3 ,V+3 ,Cr)z(Si04 h 

Kyanite . . . . . . . . . . . . . . . . . . Al2Si05 

Staurolite. . . . . . . . . . . . . . . . . (Fe,Mg)zA19Si4 0 2iOH) 

Epidote .................. Ca2 (Al,FehSi30 12(0H) 

Albite .................... NaA1Si30 8 

Sanidine ................. KA1Si30 8 

Orthoclase. . . . . . . . . . . . . . . . KA1Si30 8 

Augite . . . . . . . . . . . . . . . . . . . (Ca,Na)(Mg,Fe +z ,Al)(Si,Al)z06 

Hornblende. . . . . . . . . . . . . . . (Ca,Na)z_3 (Mg,Fe +Z ,Fe +3 ,Al)s 

(Al,Si)80 22(0H)z 

Topaz .................... Al2SiOiF,OH)z 

Oxides and hydroxides 

Hematite . . . . . . . . . . . . . . . . . Fe20 3 

Magnetite ................ (Fe,Mg)Fe20 4 

Rutile . . . . . . . . . . . . . . . . . . . . Ti02 

Limonite ................. FeO·OH·nH20 

Goethite .................. FeO(OH) 

Lepidocrocite ............. FeO(OH) 

Diaspore ................. AlO(OH) 

Phosphate minerals 

Apatite (fluorapatite) ...... Ca5(P04C03h(F,OH,Cl) 

The Role of Coal Characterization in the Control of Acid Precipitation 115 
SULFUR DIOXIDE 

NITROGEN DIOXIDE 

Figure 25.8. Nitrogen dioxide and sulfur dioxide concentration (in percent) in U.S. coal. Stippled areas represent coal 

basins. 

Table 25.4. Relation between sulfur and depositional environment in the Donetz basin, U.S.S.R. 

[From Dorofeev, 1974] 

Depositional location 

Coastal swamps on continental margin .. . ... . ...... . 

Coastal swamps on continental margin having ...... . 

weak marine influence 

Coastal swamps on marine side . .. ... . . . . .. . . . . .. . . 

Swamps having prolonged marine exposure ... ... . . . 

Typical 

sulfur 

content 

(percent) 

1.6 

2.2 

3.4 

3.9 

116 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
w 

(.) 

a: 

::::) 

0 

en 

w 

a: 

..J 

<t 

0 

(.) 

LL 

0 

1-

z 

w 

(.) 

a: 

w 

a. 

w 

> 

1-

<t 

..J 

::::) 

:E 

::::) 

(.) 

10 

IF THE COMPLIANCE STANDARD IS 

MADE MORE STRINGENT, THIS LINE 

SHIFTS TO THE LEFT, THEREBY 

EXCLUDING RESOURCES. 

IF THE STANDARD IS RELAXED, THIS 

LINE SHIFTS TO THE RIGHT, 

INCREASING RESOURCES . 

4 

POUNDS OF SULFUR DIOXIDE PER MILLION BTU 

Figure 25.9. Impact of changing the present compliance standard on Kentucky's coal resources. 

The Role of Coal Characterization in the Control of Acid Precipitation 117 
REFERENCES CITED 

Argonne National Laboratory, 1983, An analysis of proposed 

legislation to control acid rain: Argonne, Ill., Argonne 

National Laboratory ANL/EES-TM-209, 80 p. 

Armbruster, F.E., Brown, W.M., and Yokelson, D., 1983, A 

perspective on current acid rain issues: Croton-on Hudson, 

New York, Hudson Institute, 118 p. 

Averitt, Paul, 1975, Coal resources of the United States, January 

1, 1974: U.S. Geological Survey Bulletin 1412, 131 p. 

Bates, R.L., and Jackson, J.A., 1987, Glossary of geology (3d 

edition): Alexandria, Va., American Geological Institute, 

788 p. 

Brady, G., 1983, The cost of acid rain legislation: Washington, 

D.C., Council on Environmental Quality [pagination 

unknown]. 

Cobb, J.C., Currens, J.C., and Enoch, H.G., 1982, Compliance 

coal resources in Kentucky: Lexington, Ky., Kentucky 

Geological Survey, 52 p. 

Cobb, J.C., Currens, J.C., and Teoh, K.W., 1983, A probability 

model for predicting the impact of changes in the EPA 

compliance standard for sulfur emissions on the coal 

resources of eastern Kentucky: Lexington, Ky., Kentucky 

Geological Survey, 9 p. 

Committee on Atmospheric Transport and Chemical Transformation in Acid Precipitation, 1983, Acid deposition-Atmospheric processes in eastern North America-A review of 

current understanding: Washington, D.C., National Academy Press, 8 p. 

Dorofeev, A. P., 197 4, [bibliographic information unknown] as 

quoted in Neavel, R.C., 1981, Origin, petrography, and 

classification of coal, in Elliot, M.A., ed., Chemistry of 

coal utilization, second supplementary volume: New York, 

Wiley and Sons, p. 128. 

Finkelman, R.B., 1980, Modes of occurrence of trace elements in 

coal: College Park, Md., University of Maryland, unpublished Ph.D. dissertation, 301 p. 

Garbini, Susan, and Schweinfurth, S.P., 1986, A national agenda 

for coal-quality research-Symposium proceedings: U.S. 

Geological Survey Circular 979, 334 p. 

General Accounting Office, 1981, The debate over acid rain 

precipitation-Opposing views, status of research: Washington, D.C., Comptroller of the United States 8 p. and 

44-p. appendix. 

Gluskoter, H.J., 1978, An introduction to the occurrence of 

mineral matter in coal, in Bryers, R.W., ed., Ash deposits 

and corrosion due to impurities in combustion gases: 

Washington, D.C., Hemisphere Publishing Corp., p. 3-19. 

Gluskoter, H.J., Shimp, N.F., and Ruch, R.R., 1981, Coal 

analyses, trace elements and mineral matter, in Elliot, 

M.A., ed., Chemistry of coal utilization, second supplementary volume: New York, Wiley and Sons, 369-424. 

Moore, T., 1983, Tracing the pathways of atmospheric conversion: Electric Power Research Institute Journal, v. 8, no. 9, 

p. 16-27. 

National Acid Precipitation Assessment Program, 1983, Annual 

report to the President and Congress: Washington, D.C., 

Interagency Task Force on Acid Precipitation, 55 p. 

U.S. Bureau of Mines, 1974, Demonstrated coal reserve base of 

the United States on January 1, 1974: U.S. Bureau of 

Mines Mineral Industry Surveys, June 1974, 6 p. 

U.S. Department of Energy, 1981, Demonstrated reserve base of 

coal in the United States on January 1, 1979: U.S. 

Department of Energy DOE/EIA-0280(79), 121 p. 

Zukovic, Peter, Hatch, J.R., and Medlin, J.H., 1979, Assessment 

of the chemical composition of coal resources: Katowice, 

Poland, United Nations symposium on world coal resources, v. 3, p. 67-91. 

118 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
26. Overview of the Salt and Agricultural Drainage 

Problem in the Western San Joaquin Valley, 

California 

By Marc A. Sylvester 

INTRODUCTION 

Background 

Agricultural production in irrigated areas of the western San Joaquin Valley California is affected by waterlogging of soils and salt accumulation in the crop root zone 

(fig. 26.1). Since 1960, subsurface drains have been 

installed to remove water and salts from about 85,000 acres 

of affected farmland. These waters and salts are discharged 

to surface drains and irrigation-supply canals that deliver 

water to farms, wetlands, and Kesterson Reservoir within 

Kesterson National Wildlife Refuge (fig. 26.2). Water in 

the wetlands eventually discharges by surface flow or 

seepage to the San Joaquin River, which flows into the San 

Francisco Bay and delta. 

By 1982, the flow into Kesterson Reservoir was 

primarily subsurface agricultural drainage water. In 1982, 

the U.S. Fish and Wildlife Service (USFWS) noted high 

concentrations of selenium (30 parts per million (ppm), wet 

weight) in fish from Kesterson Reservoir and the San Luis 

Drain (Ohlendorf, 1984a; Saiki, 1986). In 1983, the 

USFWS noticed a fish kill in Kesterson Reservoir and the 

San Luis Drain (Saiki, 1986). In 1983 and 1984, the 

USFWS observed high incidences of mortality, birth 

defects, and decreased hatching rates in waterfowl using 

Kesterson Reservoir. These effects were attributed to selenium toxicity on the basis of the high concentrations of 

selenium in waterfowl using the reservoir (averaged greater 

than 60 ppm, dry weight) and morphological and physiological symptoms of toxicity (Ohlendorf, 1984a,b; Ohlendorf and others, 1986). Concentrations of selenium in 

waterfowl, from wetlands south of Kesterson National 

Wildlife Refuge that receive a mixture of drain water, 

irrigation supply water, and surface-return water, were 

generally intermediate to those found in waterfowl from 

Volta State Wildlife Area (averaged less than 5 ppm, dry 

weight), which does not receive drain water, and Kesterson 

Reservoir (Ohlendorf, 1984b; Ohlendorf and Hothem, 

1985). 

The main resource management questions are how 

waterlogging of soils can be prevented and how salts and 

toxic constituents, such as selenium, that have accumulated 

in the soils, water, and biota of the western San Joaquin 

Valley can be controlled to allow for continued agricultural 

use of the land without adversely affecting wildlife, human 

health, and beneficial uses of surface and ground waters. 

Role of the U.S. Geological Survey 

The role of the U.S. Geological Survey (USGS) as a 

scientific, fact-finding agency is to help provide the information that resource-management agencies (U.S. Bureau of 

Reclamation, USFWS, and State agencies) need to make 

informed and technically sound decisions to solve the salt 

and drainage problem. Since the early 1900's, the USGS 

has been studying the San Joaquin Valley and has published 

several reports about the geology, hydrology, and water 

quality of the valley. The USGS involvement in the salt and 

drainage problem began in the early summer of 1983 when 

the USFWS asked the USGS to test drainage water in the 

San Luis Drain for selenium and other constituents. Since 

then, the USGS has developed a program of interrelated and 

coordinated studies to determine the source, distribution, 

mobilization, transport, and fate of selenium and other 

constituents in the waters and soils of the western San 

Joaquin Valley. 

IMPORTANT GEOHYDROLOGIC AND 

AGRICULTURAL CONDITIONS 

A combination of factors appears to have produced 

the selenium toxicity at Kesterson National Wildlife Refuge. These factors are: 

Overview of the Salt and Agricultural Drainage Problem in the Western San Joaquin Valley, California 119 
West lands Water District 

0 40 Ml 

Figure 26.1. Location and main features of the study area, western San joaquin Valley, 

Calif. 

1. A geologic source of selenium in the Coast Ranges to the 

west (fig . 26.3). 

2. Transport of salts containing selenium from the Coast 

Ranges to the alluvial fans of the western San Joaquin 

Valley by erosion and rainfall runoff. 

3. Concentration of salts containing selenium in soils of the 

western San Joaquin Valley due to an arid climate (about 

90 inches of evaporation and less than 10 inches of 

precipitation) (fig . 26.4). 

4. Irrigation of crops by methods that are designed to flush 

salts from the soil. 

5. Accumulation of flushed salts and percolated irrigation 

water above a clay layer I 0-70 feet below land surface, 

present at certain locations in the western San Joaquin 

Valley (fig. 26.5). 

6. Installation of subsurface drainage systems to remove 

accumulated water and salts above the clay layer mentioned in No. 5. 

7. Transport of drainage water to Kesterson Reservoir via 

the San Luis Drain . 

8. Bioaccumulation of selenium in the food chain. Kesterson Reservoir did not receive large quantities of agricultural drainage water until 1981. Prior to 1981, most of 

the water delivered to Kesterson Reservoir was irrigation 

supply and surface-return water. Apparently, it took a 

year or two for selenium in Kesterson Reservoir to 

bioaccumulate in the food chain to concentrations that 

caused the toxicity observed from 1983 to present. 

INITIAL RESULTS OF THE USGS STUDIES 

Initial results of USGS studies have helped define the 

source and distribution of selenium and other inorganic 

constituents in the waters and soils of the western San 

Joaquin Valley (Devere! and others, 1984; Izbicki, 1984; 

120 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Luis National Wildlife Refuge 

Merced National Wildlife Refuge 

N 

1 

/ 

Westlands Water 

0 10 Mi 

0 10K 

Figure 26.2. Main water distribution and drainage systems and wetlands in the study area, 

western San Joaquin Valley, Calif. (see figure 26.1 for location). 

Presser and Barnes, 1984, 1985; Neil, 1986). Some of the 

specific findings follow (fig. 26.6). 

5. Selenium concentrations as high as 4,200 ppb were 

observed in water from a drain below irrigated fields 

southeast of Oro Lorna. 

i. 

1. Selenium concentrations ranged from 140 to I ,400 

parts per billion (ppb) in irrigation drainage water 

entering the San Luis Drain. 

2. Selenium concentrations were approximately 300 ppb 

in water flowing into Kesterson Reservoir from the San 

Luis Drain. 

3. The selenium concentration in pond 2 of Kesterson 

Reservoir (the inflow point from the San Luis Drain) 

was 350 ppb. 

4 . Selenium concentrations in Kesterson pond 11 (farthest 

from the inflow from the San Luis Drain) were 14 ppb 

in August 1983 and 60 ppb in December 1983 ; this 

increase indicates uptake of selenium by aquatic organisms and sediments in Kesterson Reservoir. 

6. Inflow to Grassland Water District via Agatha Canal 

and Camp 13 Ditch had selenium concentrations ranging from 45 to 65 ppb . 

7. Irrigation supply and surface-return waters and waters 

of Volta State Wildlife Area (which does not receive 

drain water) had selenium concentrations ranging from 

less than 2 to 10 ppb. 

8. Detectable concentrations of selenium (I ppb or 

greater) were found in the shallow ground water 

throughout the San Luis Drain Service Area. South of 

Los Banos, selenium concentrations generally were 

greater than 10 ppb . Selenium concentrations were 

highest in the vicinity of the Panoche fan where many 

Overview of the Salt and Agricultural Drainage Problem in the Western San Joaquin Valley, California 121 
Coast Range: 

Marine shales, siltstones, 

and sandstones 

\ Rainfall percolates into Coast Range 

~ formations and oxidizes and dissolves 

minerals containing sulfur and selenium. 

t:( Dissolved minerals move to land surface 

\ where they are removed by erosion and 

rainfall runoff. Runoff travels to 

streams that discharge to alluvial fans. 

Selenium found in association with 

and behaves chemically like sulfur. 

Figure 26.3. Conceptual model of sulfur and selenium mobilization and transport. 

sites had concentrations greater than 500 ppb, the 

highest being 3,800 ppb. Some sites near Five Points in 

the Cantua Creek fan had selenium concentrations 

between 100 and 500 ppb. Only selenium, chromium, 

boron, and mercury were detected at concentrations 

approaching or exceeding recommended guidelines for 

the protection of freshwater aquatic life or agricultural 

crops. 

9. Four of 63 wells sampled that withdraw water from the 

regional aquifer had selenium concentrations that 

exceeded 10 ppb, the U.S. Environmental Protection 

Agency's drinking-water standard. Two of 39 domestic 

~~~Less 

~ than 10" of rain per year 

1tr~-~ ·· .. ·:·· · .. l~rigation water contains sa lt 

Evaporation and transpiration remove 

water and leave salts behind 

Figure 26.4. Climate, irrigation, and drainage in the west· 

ern San Joaquin Valley, Calif. 

wells had selenium concentrations of 11 and 13 ppb. 

Two of 11 irrigations and agricultural wells had selenium concentrations of 55 and 120 ppb . 

10. Most of the shallow ground water in the San Luis Drain 

Service Area is alkaline and slightly to highly saline . 

These conditions are important, because selenium is 

very soluble when it is in an oxygenated alkaline 

environment, and under these conditions, it is very 

mobile in the aquifer and surface-water system. Thus, 

selenium can be easily transported from soils in the 

western San Joaquin Valley to subsurface tile drains, 

the San Luis Drain, and Kesterson Reservoir. 

Regional 

aquifer 

Figure 26.5. Cross-sectional sketch of western San Joaquin 

Valley, Calif., showing location of clay layers and major 

aquifers. 

122 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
I 

Nees1Ave . . , 

' \ 

\ 

\ 

Drai~age collector 

\ 

\ 

\ 

' .... _ 

..... , 

N 

1 0 

0 

' 

FRESN~ ' CD . 

\ c 

\ Three 

\ Rocks 

\ 

\ 

\ 

\ 

\ 

\ ', ' ' ' \ 

I 

I 

I 

\ 

\ 

20 Mi 

20 Km 

\ 

I 

DISSOLVED SELENIUM IN 

MICROGRAMS PER LITER 

...... ) 

I 

( 

' ---v ' /--,, 

• Less than 1 

• 1-10 

• 11-100 

• 101-500 

• More than 500 

Inflow to Kesterson Reservoir 

from the San Luis Drain 

about 300 JLQ/1 

--., 

r·-

:-.'1., 

.~ i f"• • Lr L, ! L.., 

I • .} 

' ••• t-J\..J c 1," "'\ • 1....-1 

• Stratf~rd ( 

• e: I 

' r---..J 

• KINGS CD. 

.. " 

' ' 

•I 

J 

c \Kettleman City 

Figure 26.6. Selenium concentrations in surface and ground water of the western San Joflquin 

Valley from Tracy to Kettleman City, Calif. 

Overview of the Salt and Agricultural Drainage Problem in the Western San Joaquin Valley, California 123 
11. The dominant water type is sodium sulfate, the predominant soluble salt in the bedrock of the Coast 

Ranges (fig. 26.3). This characteristic shows that 

waters in the western San Joaquin Valley were derived 

from runoff from the Coast Ranges. Thus, if the 

ultimate source of selenium is to be understood, 

geochemical studies are needed of the minerals and 

waters of the Coast Ranges, as well as such studies in 

the valley. 

12. The USGS is doing a study of trace elements in Suisun 

Bay (Luoma and others, 1984). This study was started 

in 1983. Results show that sediments in Suisun Bay 

were typical of those in San Francisco Bay-coarsegrained sands to fine silt-clay enriched in manganese 

and iron. Sediment samples have been analyzed for 

silver, lead, copper, zinc, iron, manganese, and cadmium. Clams have been analyzed for silver, copper, 

zinc, and cadmium. Clam-tissue concentrations of 

silver and zinc are similar to those found in clams from 

pristine areas. Sediment and clams collected in 1984 

and subsequent years will also be analyzed for selenium, mercury, and arsenic. 

CONTINUING USGS STUDIES 

Studies are continuing to: 

1. Confirm the source of selenium. 

2. Better define the distribution of selenium and other 

constituents in the waters and soils of the western San 

Joaquin Valley. 

3. Determine the processes controlling the mobility, transport, and fate of selenium and other constituents in the 

waters, sediments, and soils of the western San Joaquin 

Valley. 

4. Describe the geology and movement of water and 

solutes in the western San Joaquin Valley. 

5. Assess the occurrence and transport of selenium and 

other constituents in the San Joaquin River. 

6. Determine concentrations of trace elements, including 

selenium in the sediments and in selected aquatic organisms of the San Francisco Bay and delta. 

REFERENCES CITED 

Deverel, S.J., Gilliom, R.J., Fujii, Roger, Izbicki, J.A., and 

Fields, J .C., 1984, Areal distribution of selenium and other 

inorganic constituents in shallow ground water of the San 

Luis Drain Service Area, San Joaquin Valley, California-A preliminary study: U.S. Geological Survey Water 

Resources Investigations Report 84--4319, 67 p. 

Izbicki, J.A., 1984, Chemical quality of water at 14 sites near 

Kesterson National Wildlife Refuge, Fresno and Merced 

Counties, California: U.S: Geological Survey Open-File 

Report 84-582, 14 p. 

Luoma, S.N., Cascos, P.V., and Dagovitz, R., 1984, Trace 

metals in Suisun Bay, California-A preliminary report: 

U.S. Geological Survey Water Resources Investigations 

Report 84--4170, 39 p. 

Neil, J .M., 1986, Dissolved-selenium data for wells in the western 

San Joaquin Valley, California, February to July 1985: 

U.S. Geological Survey Open-File Report 86-73, 12 p. 

Ohlendorf, H.M., 1984a, The biologic system, in Conference on 

toxicity problems at Kesterson Reservoir, summary report 

prepared for the Mid-Pacific Region, U.S. Bureau of 

Reclamation: Lafayette, Calif., Ecological Analysts Inc., 

p. 8-16. 

---1984b, Summary of research status and results-Kesterson 

National Wildlife Refuge and the Grasslands, presented at 

the Flyway "Grasslands" San Joaquin Valley Chapter, 

Wildlife Society Meeting: Davis, Calif., University of 

California, U.S. Fish and Wildlife Service, Patuxent Wildlife Research Center, Pacific Coast Field Section, Wildlife 

and Fisheries Biology, 5 p. 

Ohlendorf, H.M., Hoffman, D.J., Saiki, M.K., Aldrich, T.W., 

1986, Embryonic mortality and abnormalities of aquatic 

birds-Apparent impacts of selenium from irrigation drainwater: Science of the Total Environment, v. 52, p. 49-63. 

Ohlendorf, H.M., and Hothem, R.L., 1985, Preliminary summary, selenium in birds nesting in the Grasslands . of 

western Merced County: Davis, Calif., University of California, U.S. Fish and Wildlife Service, Patuxent Wildlife 

Research Center, Pacific Coast Field Section, Wildlife and 

Fisheries Biology, 7 p. 

Presser, T.S., and Barnes, Ivan, 1984, Selenium concentrations in 

waters tributary to and in the vicinity of the Kesterson 

National Wildlife Refuge, Fresno and Merced Counties, 

California: U.S. Geological Survey Water Resources Investigations Report 84--4122, 26 p. 

---1985, Dissolved constituents including selenium in waters 

in the vicinity of Kesterson National Wildlife Refuge and 

the West Grassland, Fresno and Merced Counties, California: U.S. Geological Survey Water Resources Investigations Report 85--4220, 73 p. 

Saiki, M.K., 1986, A field example of selenium contamination in 

an aquatic food chain, in Proceedings of symposium on 

selenium in the environment, June 10-12, 1985, Fresno, 

Calif.: Fresno, Calif., California State University, California Agricultural Technology Institute Publication No. 

CAT1/860201, p. 67-76. 

124 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
27. A Potential Source Area for Selenium and 

Mercury in Agricultural Drainage Water at 

Kesterson Reservoir, San Joaquin Valley, 

California 

By Ronald R. Tidball, R.C. Severson, james M. McNeal, and Stephen A. Wilson 

Abstract 

Agricultural drainage water collected from the San 

Luis Unit of the Federal Central Valley Project irrigation 

development on the west side of the San Joaquin Valley, 

Calif., has been channeled through the San Luis Drain 

canal into an evaporation reservoir in the Kesterson 

National Wildlife Refuge. The water, plants, sediments, 

and aquatic life contain high levels of selenium, which is 

believed to be responsible for a high incidence of mortality among nesting birds in the area (U.S. Bureau of 

Reclamation, 1984). Analyses of several hundred soil samples from throughout the San Joaquin Valley and the San 

Luis Drain Service Area on the west side of the valley show 

there are two major anomalous areas for selenium-the 

Panoche-Cantua Creek alluvial fans in the service area in 

western Fresno County and the Antelope Hills in western 

Kern County. There is one major anomaly for mercury-the Panoche-Cantua Creek area. Soil samples from 

the service area indicate that the selenium source area is 

in the vicinity of Monocline Ridge on a mudflow deposit 

between Panoche fan and Cantua fan. The higher mercury 

values on both Panoche Creek and Cantua Creek fans 

indicate alluvial dispersion trains that originate in the New 

ldria mercury district about 20 miles upstream. 

INTRODUCTION 

Surface irrigation water was first imported into the 

San Joaquin Valley from the north when the Delta-Mendota 

Canal commenced operation in 1951 under the Federal 

Central Valley Project. The San Luis Unit, the most recent 

area to be developed on the west side of the San Joaquin 

Valley in western Fresno, Merced, and Kings Counties, 

Calif., first received water through the Delta-Mendota and 

the San Luis canals in 1967 (San Joaquin Valley Interagency Drainage Program, 1979). Soils in the area have long 

been notable for adverse salinity conditions and a high 

water table especially near the valley trough (Mendenhall 

and others, 1916). To mitigate these conditions, the San 

Luis Drain, a concrete-lined canal that borders the lower 

edge of the San Luis Unit (San Luis Drain Service Area; fig. 

27. 1), hereafter referred to as the service area, was constructed between 1968 and 1975. The canal extends for 82 

miles from a point just east of Five Points in Fresno County, 

Calif., to Kesterson National Wildlife Refuge in Merced 

County near Gustine, Calif. Kesterson Reservoir was orig-

----------, 

N 

l 

I 

I 

I 

I 

I 

I 

I 

I 

l... San Luis ' 

Drain Service ', 

Area '-. 

.. - --, ', dl ~., ', ' \ ' ·: .. "0 \. ' • ~!). ', ' 

~..; \ " .·. t. \ ', 

::· ~~ ', "' 

\ ~ \ ' \ \ ' \ ',._ _ _j \ " I, 

---

~) / 

\ 

r' 

I 

~ -----J 

Figure 27.1. Map of California showing location of study 

area-San Luis Drain Service Area, Panoche fan, and San 

joaquin Valley, Calif. 

A Potential Source Area for Selenium and Mercury in Agricultural Drainage Water, Kesterson Reservoir, Calif. 125 
inall y intended to be a regulating reservoir for the canal, 

which was to extend to the San Joaquin-Sacramento River 

delta for discharge. However, the canal was never finished, 

and Kesterson Reservoir, which is a series of 12 ponds 

covering 1,280 acres, became the temporary terminus. Salts 

have accumulated in the ponds because the only outlet is 

through evaporation or seepage. 

The purpose of this study was to discover the geologic source of the trace elements that are causing toxic 

conditions at Kesterson. We determine that source by 

identifying, with an areal survey of element distribution in 

soils, those localities having geochemical anomalies as 

compared to a background level. This report shows the 

distribution of selenium in soils and its potential geologic 

source. We also include the distribution of mercury because 

a world-class mercury mineralization district is located in 

the Diablo Range adjacent to the service area. 

METHODS 

Field and laboratory methods have been described by 

Tidball and others ( 1989). Data handling has been described 

by Tidball and others (1986). In 1983, soils were sampled 

throughout the San Joaquin Valley at 297 sites about 10 km 

apart. These valley samples represent a composite sample 

of the 0- to 12-inch (0- to 30-cm) depth of the soil. In 1985, 

soils were also sampled on the Panache-Cantua Creek fan 

area at 721 sites 1 mile apart. The Panache samples 

represent a composite sample of the 66- to 72-inch (168- to 

183-cm) depth of the soil. The clay fraction (less-than2-mm size fraction) of all samples was analyzed for total 

concentrations of selenium by hydride generation and 

atomic-absorption spectrophotometry (Briggs and Crock, 

1986) and for total mercury by cold-vapor atomicabsorption spectrophotometry (Kennedy and Crock, 1987). 

The observed data points were used as the basis for 

estimating a grid of points by kriging (Tidball and others, 

1986). The grid for the valley soils, which were collected at 

about 10-km intervals, was estimated at 2-km intervals. The 

grid for the Panache samples, which were collected at 

1-mile intervals, was estimated at 0.5-km intervals. A 

gray-scale display was compiled from the gridded data. 

RESULTS 

The distribution map of selenium in the valley (fig. 

27 .2) shows that above-average selenium values are found 

on the west side of the valley and below-average values on 

the east side. Thus the granitic terrane of the Sierra Neva~a, 

which provided the valley-fill sediments for the eastern part 

of the valley, is an insignificant source of selenium. The 

overall pattern indicates the presence of a broad-scale but 

moderate-level source of selenium on the west side within 

or at the edge of the Diablo Range. Once the overall 

perspective is available, it is readily apparent that certain 

localities stand out as anomalies. Those localities include 

the Panache-Cantua Creek fans in the service area, the 

Antelope Hills in western Kern County, and Maricopa Flat 

in southwestern Kern County. In all three areas, the 

anomalies border on sedimentary rocks that range from 

marine units of Cretaceous age through nonmarine units of 

Quaternary age. The map showing mercury distribution in 

the valley soils (fig. 27. 3) indicates that a significant 

mercury anomaly is located in the Panache-Cantua Creek 

area. Three less significant anomalies are found along the 

west and south sides of the valley. 

The detailed map of selenium in Panoche samples 

(fig. 27.4) shows that selenium is not associated with either 

of the two larger present-day alluvial fans of Panoche and 

Cantua Creeks but is on an interfan area bordering Monocline Ridge. The interfan area is likely to be composed of 

coalescing alluvial fans that are overlain by mudflow 

deposits near the foothills. The mudflows were probably 

derived from sedimentary rocks of one or more of the 

adjacent formations-the nonmarine Tulare Formation, the 

marine Etchegoin Formation, the marine Kreyenhagen 

Shale, and perhaps other formations further back into the 

foothills. 

The map showing mercury distribution in the Panoche samples (fig. 27 .5) indicates that mercury is associated 

with the alluvial sediments of both Panoche Creek and 

Cantua Creek. A major mercury mineralization district is 

located along the New Idria fault that flanks a large 

intrusive body of ultrabasic rocks near the town of Idria. 

The New Idria mine was the second largest producer of 

mercury in North America between 1858 and 1972. Other 

smaller mines are scattered throughout the district. Streams 

that drain the north, east, and south sides of the district all 

have outwash fans in the valley. Panache Creek fan, which 

drains the north side of the district, exhibits the most 

prominent dispersion train for mercury, followed by the 

Cantua Creek fan, which drains the east side. 

DISCUSSION 

The location of the source area of selenium is clearly 

in or near the San Luis Drain Service Area. The ultimate 

host material for selenium is unknown at this time, but for 

the present the soil and the ground water are a repository for 

selenium. Undoubtedly, deeper sediments also contain 

selenium. A source area in the vicinity of Monocline Ridge 

would suggest that one or more sedimentary-rock strata are 

the host rocks. Based on a common type of occurrence of 

selenium in other parts of the west, the host may be a shale 

of marine origin. Lakin and Byers (1941) found 28 parts per 

million (ppm) selenium in the marine Moreno Shale in the 

126 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Percentile Se, ppm 

0 0.07 

+ + 10 .09 

+ + 

30 . 11 

50 .13 

70 .18 

90 .36 

95 .59 

+ 99 .88 +87" 

100 1.07 

() 

~ Panoche Fan 

~( Study 0 

+ + + + 

-?"1 

~Q ~ 

8d~ + + +SS" 

~ ANTELOPE HILL 

+ + + 

IS' 

o""-1- ~ 

40 0 40 Ml "ll'.:GI I I I o"ll' 

40 0 40 KM 

86~ + + + +86" 

IJH" tzrr 

MARICOPA 

FLAT 

Figure 27.2. Distribution of selenium at 0- to 12-in. depth of soils in the San joaquin Val ley, Calif. Shades of gray delineate 

percentiles of the distribution of median values for each 2-km cell . ppm, parts per million. 

A Potential Source Area for Selenium and Mercury in Agricultural Drainage Water, Kesterson Reservoir, Calif. 127 
+ 

+ 

87"+ 

() Panoche Fa 

"-'"'1 Study Are 

~< 

+ 

0 

+ 

-9"'1 

1-Q ~ 

+ + 

+ + + 

40 0 40 Ml 

I 

I 

40 0 40 KM 

86"+ + + Ill" 

tzo• 

+ 

+ 

+ 1ZO" 

+ 119° 

+ 

Percentile Hg, ppb 

+ 

+ 

MARICOPA 

FLATS 

0 

10 

30 

50 

70 

90 

95 

99 

100 

14 

17 

19 

22 

27 

38 

55 

170 

330 

+ 

+ 38" 

+ 

+ 87° 

+ 

+ 

Figure 27.3. Distribution of mercury at 0- to 12-in. depth of soils in the San joaquin Valley, Calif. Shades of gray delineate 

percentiles of the distribution of median values for each 2-km cell. ppb, parts per billion. 

128 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
120•46' 

.97"+- + 

+ 

SS•46'+ 

+ 

% 

+ + 

10 

I I 

10 

+ 

0 

I 

0 

+ 

120"30' 

+ + 

+ 

I 0 Ml 

I I 

I 0 KM 

+ + t.Jo•ao• 

1BO•t6' 1zo• 

+ + +sr 

Percentile Se, ppm 

0 0.05 

10 .32 

+ 30 .62 + 

50 . 79 

70 .89 

90 1.13 

+ 95 1.34 + 36.46' 

99 1.83 

100 2.38 

+ + 

eHELM 

FIVE POINTS 

+ + 

+ + + 3fJDf6' uo•ts• fJ!D• 

Figure 27.4. Distribution of selenium at 66- to 72-in. depth of soils in the Panache-Cantua Creek fan area , San Luis Drain 

Service Area, Calif. Shades of gray delineate percentiles of the distribution of median values for each 2-km cel l. ppm, 

parts per million . 

Diablo Range about 65 miles northwest of Monocline 

Ridge. The proximity of the mercury mineralization district 

at New Idria, as well as hints of an association of selenium 

with other ultrabasic intrusives in the southern part of the 

valley, is either a remarkable coincidence, or it suggests 

that selenium and mercury were deposited by a common 

process. A possible explanation is that, even though selenium may be hosted in a sedimentary unit, the ultimate 

source of selenium may be the hydrothermal solutions that 

were associated with these intrusives or with nearby faults. 

SUMMARY 

It appears that selenium, which is bioaccumulating in 

plants and fauna in the Kesterson Reservoir area, was 

transported to the reservoir with other soluble salts in 

agricultural drainage water from saline soils and ground 

waters located in the San Luis Drain Service Area in 

western Fresno County. The geomorphic setting of the 

service area is the Panache-Cantua Creek fans, which abut 

down-dipping sedimentary rock strata at the mountain front. 

A Potential Source Area for Selenium and Mercury in Agricultural Drainage Water, Kesterson Reservoir, Calif. 129 
120'46' 120'30' 120'16' 120' 

.97'r + + + + + + + 8'1' 

Percentile Hg, ppb 

0 14 

10 17 

+ + + 30 30 + 

60 59 

70 107 

90 172 

96'.1.5~ 95 211 + 36'46' 

99 311 

100 566 

+ + + 

• SAN JOAQUIN 

HELM 

• se•so~ + + + 86'80' 

% 

+ + + + 

10 0 I 0 Ml 

I 

I I I 

I 

10 0 I 0 KM 

38'15~ + + + + + + + 36'16' 

120"46' 120'.90' uo•ts' 1ZO' 

Figure 27.5. Distribution of mercury at 66- to 72-in. depth of soils in the Panache-Cantua Creek fan area, San Luis Drain 

Service Area, Calif. Shades of gray delineate percentiles of the distribution of median values for each 2-km cell. ppb, parts 

per billion. 

A major source of selenium is in the vicinity of Monocline 

Ridge and may result from local mudflow deposits rather 

than alluvium from within the interior of the Diablo Range. 

Although the present repository of selenium is in the soils, 

sediments, ground water, and perhaps nearby sedimentary 

rock units, the ultimate source of selenium may be associated with the same geological processes that were responsible for the major mercury mineralization zone at New 

Idria about 20 miles southwest of the service area . 

REFERENCES CITED 

Briggs, P.H., and Crock, J.G., 1986, Automated determination of 

total selenium in rocks, soils, and plants: U.S. Geological 

Survey Open-File Report 86--40, 20 p. 

Kennedy, K.R., and Crock, J.G., 1987, Determination of mercury in geological materials by continuous flow, coldvapor, atomic absorption spectrophotometry: Analytical 

Letters, v. 20, p. 899-908. 

130 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Lakin, H.W., and Byers, H.G., 1941, Selenium occurrence in 

certain soils in the United States, with a discussion of 

related topics; 6th report: U.S. Department of Agriculture 

Technical Bulletin 783, 27 p. 

Mendenhall, W.C., Dole, R.B., and Stabler, Herman, 1916, 

Groundwater in San Joaquin Valley, California: U.S. 

Geological Survey Water-Supply Paper 398, 310 p. 

San Joaquin Valley Interagency Drainage Program, 1979, Agricultural drainage and salt management in the San Joaquin 

Valley, final report including recommended plan and firststage environmental impact report: Fresno, Calif., San 

Joaquin Valley Interagency Drainage Program, 165 p. 

Tidball, R.R., Grundy, W.D., and Sawatzky, D.L., 1986, Kriging techniques applied to element distribution in soils of the 

San Joaquin Valley, California, in Proceedings, 

HAZTECH INTERNATIONAL, Hazardous Materials 

Management Exhibition and Conference, Denver, Colo., 

August 13-15, 1986: Chicago, Ill., Pollution Engineering 

Magazine, p. 992-1009. 

Tidball, R.R., Severson, R.C., Gent, C.A., and Riddle, G.O., 

1989, Element association in soils of the San Joaquin 

Valley of California, chap. 9, in Jacobs, L.W., and others, 

eds. , Selenium in agriculture and the environment: Soil 

Science Society of America Special Publication 23. 

U.S. Bureau of Reclamation, 1984, Kesterson Reservoir and 

waterfowl: U.S. Bureau of Reclamation Information Bulletin 2, 11 p. 

A Potential Source Area for Selenium and Mercury in Agricultural Drainage Water, Kesterson Reservoir, Calif. 131 

28. Geoelectrical Studies on the Panoche Fan Area 

of the San joaquin Valley, California 

By Robert J. Bisdorf 

INTRODUCTION 

In 1985, the U.S. Geological Survey made 82 

Schlumberger direct current resistivity soundings and ran 18 

electromagnetic profiles in the Panoche fan area of California. The Panoche fan is located in the central section of the 

San Joaquin Valley, west of Mendota, Calif. (fig. 28.1). 

The geoelectrical studies were part of a larger effort to study 

sources of selenium and selenium contamination of ground 

water. Deverel and others ( 1984) reported high levels of 

selenium in shallow ground-water samples at the edges of 

the fan. Of particular hydrologic interest is the presence or 

absence of a clay layer, usually in the upper 100 m, that 

creates a perched aquifer in parts of the fan. It is possible 

that the clay layer contributes to high selenium concentrations by not allowing irrigation waters to percolate downward. The geoelectrical studies were designed to detect the 

presence or absence of this clay layer. 

GEOELECTRICAL SURVEY 

Schlumberger soundings were chosen as the main 

geophysical tool because of their long history of successful 

application in ground-water studies. The Geonics EM-34, 

an electromagnetic geophysical tool, was used at 18 sites to 

evaluate its usefulness for further studies. Only the Schlumberger sounding data and interpretations are presented in 

this report. Figure 28.1 shows the location and identifying 

number of the 82 Schlumberger soundings. 

Schlumberger sounding is a direct-current resistivity 

technique that involves injecting current into the ground 

through two metal electrodes (A and B) and measuring the 

electric field with two other electrodes (M and N) centrally 

located between the A and B electrodes. An apparent 

resistivity is calculated by using a formula that relates the 

measurement made with the M and N electrodes, the 

amount of current injected into the ground, and the distances between the A-B and M-N electrode pairs (Zohdy 

and others, 197 4). The A and B electrodes are moved 

successively to larger separations to probe deeper. Figure 

28.2 shows two typical Schlumberger sounding curves, 

Panoche 50 and Panoche 56, whose locations are indicated 

by the asterisks on figure 28 .1. Sounding Panoche 50 

indicates the presence of higher resistivity material than 

does sounding Panoche 56. Schlumberger soundings are 

usually interpreted as a series of horizontal layers of varied 

resistivities and thicknesses. The Panoche fan sounding data 

were interpreted by using a program by Zohdy (1974), 

modified to run on a desktop computer using a more precise 

set of linear filter coefficients developed by O'Neill (1975). 

RESISTIVITY MAPS 

To show the areal distribution of resistivity, maps of 

interpreted resistivity at a particular depth were generated 

by determining, for each sounding, the interpreted resistivity at that depth. These data and the x-y coordinates of each 

sounding were put into a gridding program (We bring, 

1981), and the output was contoured. Maps of interpreted 

resistivity at depths of 5, 10, and 20 m are presented as 

figures 28.3, 28.4, and 28.5, respectively. Each map can be 

thought of as looking at a slice of the Earth's resistivity 

distribution at that depth. 

In the forthcoming discussion of the interpreted 

resistivity maps, the following assumptions and interpretive 

criteria are used. Resistivities greater than 20 ohm-m 

represent relatively coarse-grained material (sand-gravel) 

and as such will probably exhibit high porosity and (or) 

permeability. Resistivities less than 7 ohm-m represent 

relatively fine-grained materials (clay). The lower the 

resistivity, the larger the proportion of clay. These criteria 

assume that the ground-water quality is about the same over 

the area of interest; this probably is a valid assumption, 

especially in the upper 50 m, because the major source of 

shallow ground water is irrigation water from the California 

aqueduct. If this assumption is not valid, then the resistivities may be ground-water salinity indicators as well as, or 

instead of, lithologic indicators. The results of water sampling may validate this assumption. 

Soundings Panoche 50 and 56, as shown in figure 

28.2, indicate the response of Schlumberger soundings to 

Geoelectrical Studies on the Panoche Fan Area of the San joaquin Valley, California 133 
Figure 28.1. Location and identifying number of the Schlumberger soundings, Panoche fan area, California. Asterisks 

indicate locations of soundings whose curves are shown in figure 28.2. 

Vl 

"'o 

~~ -----------.-----------.----------,-----------

::> I 

I 50 I 

::> 

I 

0 

"" 

,__ 

z 

w 

0: 

i I ---- -·-··- ··- ·· - ··--··-j·- ··- ··- ------ ··-··-··---- ,------ -·- ··-

0-o--o-) - "- - ~(}-() ~--v-----'1 

I . PANOCHE 56 

~~ --------~-----------L----------~--------~ 

~ 1 1 0 I 00 1 000 1 0000 

SCHLUMBERGER ELECTRODE SPACING (AB/2), IN METERS 

~ Figure 28.2. Two typical Schlumberger sounding 

curves, Panoche fan area, California. Sounding Panoche 50 shows the response to higher resistivity material, and sounding Panoche 56 shows the response to 

the lower resistivity material. The locations of these 

soundings are highlighted on figure 28.1 with asterisks . 

134 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Figure 28.3. Contour map of interpreted resistivity at a depth of 5 m, Panache fan area, California. The dot pattern 

indicates areas of resistivities of greater than 20 ohm-m. The stipple pattern indicates areas of resistivities of less than 7 

ohm-m. Contour values are in ohm-m. 

the presence of coarse- and fine-grained material. Sounding 

Panache 50 is located in an area having resistivities greater 

than 20 ohm-m in the upper 80 m; these values indicate the 

presence of relatively coarse-grained material. Sounding 

Panache 56 is located on the margin of the fan where the 

resistivities are less than 7 ohm-m in the upper 80 m; these 

values indicate the presence of relatively fine-grained material. 

Figure 28 .3 shows the resistivity map for a 5-m 

depth. It is interesting to note that the lower center of the 

map, roughly corresponding to the center of the fan, has a 

zone of resistivities of greater than 20 ohm-m and that the 

edges of the map show resistivities of less than 7 ohm-m. 

This contrast indicates that the center of the fan is composed 

of relatively coarse-grained material and that the edges of 

the fan have a high percentage of clay. The parts of the map 

that show resistivities between 7 and 20 ohm-m are in an 

intermediate zone where the composition is probably 

mixed. Other information will be needed to classify these 

areas. 

Figure 28.4 shows the resistivity map for a 10-m 

depth. As in the map for a 5-m depth, this map shows that 

the center of the fan is composed of mostly coarse-grained 

material and the edges are composed of mostly clay. The 

high-resistivity zone in the center of the fan extends 

southwest toward the mouth of Panache Creek and indicates 

Geoelectrical Studies on the Panoche Fan Area of the San joaquin Valley, California 135 
Figure 28.4. Contour map of interpreted resistivity at a depth of 10 m, Panoche fan area, California. The dot pattern 

indicates areas of resistivities of greater than 20 ohm-m. The stipple pattern indicates areas of resistivities of less than 7 

ohm-m. Contour values are in ohm-m. 

that the coarse-grained material may be related to the 

Panoche Creek drainage. 

Figure 28.5 shows the resistivity map for a 20-m 

depth. Again the center of the fan shows high resistivities 

and indicates mostly coarse-grained material. The edges of 

the fan seem to be composed of clay , and it seems that the 

northern edge of the fan is somewhat lower in resistivity at 

this depth than at the other depths; this value indicates a 

higher clay content. The intermediate resistivities are less 

prevalent at this depth, and as the high-resistivity zone did 

not increase in area, the low-resistivity zone has gotten 

larger. This trend continues on the maps of depths greater 

than 20 m, which are not presented here . 

CONCLUSIONS 

Schlumberger soundings appear to map the presence 

or absence of clays, at least in a gross sense, in the Panoche 

fan area. In general, the center of the fan appears to have 

much less clay than the edges. In addition, the coarsegrained central fan area appears to be related to the Panoche 

Creek drainage. This makes sense as the Panoche Creek 

probably transported whatever coarse material there was. 

Resistivity maps not presented here indicate that the coarsegrained material appears to disappear at depths greater than 

200 m. This disappearance may be real or higher salinity 

ground water may be masking the presence of the coarse136 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Figure 28.5. Contour map of interpreted resistivity at a depth of 20 m, Panache fan area, California. The dot pattern 

indicates areas of resistivities of greater than 20 ohm-m. The stipple pattern indicates resistivities of less than 7 ohm-m. 

Contour values are in ohm-m. 

grained material. The assumption of uniform ground-water 

quality may not be valid at depths greater than 50 m. 

REFERENCES CITED 

Devere!, S.J., Gilliom, R.J., Fujii , Roger, lzbicki , J.A. , and 

Fields, J .C., 1984, Areal distribution of selenium and other 

inorganic constituents in shallow ground water of the San 

Luis Drain service area, San Joaquin Valley, California-A 

preliminary study: U.S. Geological Survey WaterResources Investigations Report 84-4319, 67 p. 

O'Neill, D.J., 1975, Improved linear filter coefficients for application in apparent resistivity computations: Australian Society of Exploration Geophysics Bulletin, v. 6, no. 4 , 

p. 104-109. 

Webring, Michael, 1981, MINC-A gridding program based on 

minimum curvature: U.S. Geological Survey Open-File 

Report 81-1224, 43 p. 

Zohdy, A.A .R., 1974, A computer program for the automatic 

interpretation of Schlumberger sounding curves over horizontally stratified media: U.S. Department of Commerce, 

Springfield, Va. , National Technical Information Service 

Report PB-232 703/AS, 25 p. 

Zohdy, A.A.R., Eaton, G.P. , and Mabey, D.R. , 1974, Application of surface geophysics to ground-water investigations: U.S. Geological Survey Techniques of Water 

Resources Investigations, book 2, chap. Dl, 116 p. 

[Reprinted 1980 .] 

Geoelectrical Studies on the Panoche Fan Area of the San Joaquin Valley, California 137 

29. Initial Shallow Seismic Tests in the Panoche Fan 

Area, Fresno County, California 

By Wilfred P. Hasbrouck 

INTRODUCTION 

During April 1985, the U.S. Geological Survey 

conducted seismic tests at four widely spaced sites on the 

Panoche fan, Fresno County, Calif., to develop a relatively 

inexpensive, high-resolution, reflection method that can be 

used to map a clay layer at a depth of less than 100m. Both 

longitudinal- (P-) and shear- (S-) wave procedures were 

investigated. The primary source of seismic energy was a 

9.1-kg hammer struck vertically against a 15-cm2 aluminum 

plate or horizontally against a steel fixture pinned to the 

ground with eight spikes. Seismic arrivals were detected by 

40-Hz seismometers whose outputs were linked through an 

interface unit to a 12-channel, signal-enhancement engi-

(J) 

0 

z 

0 

u 

U-1 

(J) 

:::::i 

....J 

~ 

neering seismograph and digitally stored on magnetic tape. 

All data processing was done on a desktop computer. 

SPOT-TEST RESULTS FROM SEISMIC SITE 1 

Shear-wave reflections were detected on wave tests, 

and spot tests taken at seismic site 1 (NW comer, NEl/4 

sec. 25, T.13 S., R.12 E.), near location 53 of Bisdorf's 

Schlumberger direct-current resistivity survey (Bisdorf, this 

volume, fig. 28.1). Three radial-source/radial-seismometer, 

shear-pair seismograms obtained along this line are shown 

in figure 29 .1. Arrivals that have a convex alignment 

(dashed line) and are centered at 450 ms have the charac500 24 9 12 27 24 9 12 27 24 9 12 27 

OFFSET, METERS 

Figure 29.1. Three radial-source/radial-seismometer, shear-wave, spot-test seismograms 

from seismic site 1, Panoche fan area, California. The dominant arrival at about 450 ms 

(dashed line) has the characteristics of a seismic event reflected from a horizon at a depth 

of approximately 36m. SP, shot point. 

Initial Shallow Seismic Tests in the Panoche Fan Area, Fresno County, California 139 
SP 101 

91 109 

- t-- ----,-- - t-- ;- -- -

750 

30 15 12 27 30 15 12 

OFFSET, METERS 

27 30 15 12 27 

Figure 29.2. Three radial-source/radial-seismometer, shear-wave, spot-test seismograms 

from seismic site 3, Panoche fan area, California. Suggestions of a reflected event occur 

at250 ms (dashed line), an estimated horizon depth of20 m, on the record from shot point 

(SP) 29. 

teristics of seismic reflections. Using a velocity of 160 m/s, 

obtained from analysis of a series of velocity panels, the 

computed depth of this seismic horizon is 36 m. 

At electrical site 53, Bisdorf's soundings (personal 

commun.) indicate that the top of a low-resistivity layer of 

4 ohm-m (a clay?) occurs at a depth of 12 m and the 

electrical section maintains a resistivity of less than 7 

ohm-m to a depth of more than 1,000 m. No significant 

change in resistivity was observed at a depth of 36 m. 

SPOT-TEST RESULTS FROM SEISMIC SITE 3 

Shown on figure 29.2 are spot-test results obtained at 

seismic site 3, near location 68 of the electrical survey 

(Bisdorf, this volume, fig. 28.1), and 7.3 km east and 3.3 

km south of seismic site 1. Spot-test responses at seismic 

sites 1 and 3 clearly are not the same, implying that the 

stratigraphic sections differ-as would be expected in a fan 

environment. Near-surface rocks at seismic site 3 have a 

higher velocity (as evidenced by less time for the first 

reflection arrivals), and the dominant reflection seen at 

about 450 ms at site 1 is not present. A suggestion of a 

reflection event at approximately 250 ms is shown by the 

dashed lines on the seismograms taken at shot points (SP's) 

23 and 29. 

At electrical site 68, Bisdorf's soundings (personal 

commun.) indicate that the top of a low-resistivity layer of 

5 ohm-m (a clay?) occurs at a depth of 7.5 m and that an 

increase in resistivity to 19 ohm-m is found between 16.4 to 

24.4 m, beyond which the electrical section exhibits resistivities ranging from 10 to 4 ohm-m. Clearly, seismic sites 

1 and 3 are geophysically dissimilar. 

SEISMIC SECTION AT SITE 1 

To see if the high-quality reflection events obtained 

on spot tests at seismic site 1 persist laterally, a line of 112 

shear-wave seismic records was taken and processed with a 

sixfold, common-midpoint procedure. From inspection of 

this seismic section, shown on figure 29.3, the near surface 

at site 1 appears to be composed of relatively flat, discontinuous beds and lenticular bodies. The lower reflection 

horizon (lower arrow on fig. 29. 3) appears to carry across 

the section and exhibits gentle stepping down to the west 

(left side). The display of figure 29.3 is an unmigrated time 

section, not a depth section, and an increase in average 

velocity of less than 7 percent would be sufficient to reverse 

the apparent westward dip. In general, velocity increases 

with grain coarseness within a clastic section; therefore, a 

velocity increase westward toward the source of the fan is a 

reasonable expectation. Although the average velocity may 

140 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
COMBINED-TRACE, COMMON MIDPOINT SECTION Line 1; az=90 Site: 1 PANOCHE FAN 

RAD. HAMMER (90/270) R DETECTOR Spread: -30, -15, 12, 27 Date: 111/1985 

SI•1.00ms FILTERS: 0 BGM•10 to 70K NMO VEL•.16m/ms MAX FOLD•6 9-PT SMOOTHED 

POSITION NUMBERS AT MIDPOINTS (PN INT•1.5m) 

21.5 31.5 41.5 51.5 61.5 71.5 81.5 91.5 101.5 111.5 121.5 

rJ) 

0 

z 

0 

u 

L.LJ 

rJ) 

::::i 

....J 

~ 

FOLD 

Figure 29.3. Radial-source/radial-seismometer, shear-wave, 

combined-trace, common-midpoint (CMP) section at seismic site 1, Panoche fan area, California. Horizontal distance between the traces is 3 m, total section distance is 

165 m, and depth using a constant velocity of 0.16 km/s 

change from one end of the section to the other, it is highly 

unlikely that significant velocity differences occur within 

the 3-m spacing between traces on the section. Thus, the 

lenslike appearance of the seismic traces of the lower 

horizon at positions 91.5 to 111.5 (a distance of 30 m) is 

probably real. If it is, note that, with this shear-wave 

seismic method, we are detailing a structure that has a relief 

of only about 1 m. 

It is tempting, but very unwise without drill data, to 

infer that the interpreted seismic horizon at a depth of about 

15 m (upper arrow on fig. 29.3) and the top of the 

low-resistivity layer at about the same depth are geophysical 

expressions of the clay layer. If this horizon is the top of a 

clay layer, then the seismic section indicates that the clay is 

discontinuous across the section, in contrast to the reflection 

horizon beneath it at about 200 ms. 

The block of reflection arrivals at about 260 ms and 

ranging from position 52 to 100 appears to be separated 

from its neighbors. If minor faulting occurred in this 

immediate area, then the zones of amplitude loss bounding 

this block of reflections can be interpreted as fault indicaranges from 8 to 56 m (a vertical exaggeration of approximately 2:1). Amount of fold applied in the CMP process is 

indicated on the fold diagram across the bottom of the 

section. 

tors. A fault of small throw can be interpreted downward 

and to the left from position 63.5 at 120 ms to the zone of 

low amplitude at 250 ms and a position between 45.7 and 

4 7. 5. A more likely interpretation is that lateral changes in 

seismic character result from stratigraphic variations. 

COMMENTS 

The Panache fan is almost featureless and is heavily 

farmed. Thus, traditional stratigraphic studies of it are 

restricted to what can be seen at its edges and to what can 

be observed from borehole logs. It would be prohibitively 

expensive to seismically survey the entire fan; however, for 

those problem areas within which detailed stratigraphic 

correlation between boreholes is critical, seismic results of 

the quality shown on figure 29.3 would be helpful. 

The question as to what changes in physical properties occur within this section will remain unresolved until 

borehole data have been obtained. Of particular interest in 

the seismic studies is the probable acoustic difference 

Initial Shallow Seismic Tests in the Panoche Fan Area, Fresno County, California 141 
leading to a shear-wave reflection from the clay layer. I 

suspect that the clay layer will prove to be of lower velocity, 

following the generality that finer grained clastics have 

lower velocities than coarser grained clastics. If this is true, 

then refraction methods, because they require a high-speed 

layer as a target, are not recommended for mapping the clay 

layer. Reflection methods require existence of differences 

in acoustic impedance (the product of velocity and density) 

across boundaries, a condition that may be met by a clay 

layer sandwiched between layers of coarse-grained sediments. 

P and S waves, in addition to their differences in 

particle motion, differ in their seismic behavior within the 

Earth. Within a section of unconsolidated rocks, the top of 

the saturation zone probably will be detected by P-wave 

methods, but this hydrologic boundary will be transparent 

to S-wave techniques. In broad terms, S waves respond to 

differences in lithology, whereas P waves respond to 

differences in both lithology and fluid content. For study of 

the near-surface section, it seems that the best course is to 

more fully investigate use of both methods in combination, 

an extra benefit being derived through use of vplvs ratios to 

obtain a measure of rock strength. 

As Bisdorf (this volume) has pointed out, electrical 

resistivity in this area appears to be a function of grain size, 

lower values of resistivity being associated with the finer 

grained materials. If a triple functional relationship can be 

established between stratigraphy, resistivity, and velocity in 

this area, then two possibilities emerge: 

1. Combined use of electrical and seismic methods may be 

used to map interborehole stratigraphy-in particular, 

the distribution of the clay layer and the location of old 

stream channels that may act as pathways for contaminated waters. 

2. The resistivity maps may be used to delimit lateral 

velocity variations and thus. permit time sections to be 

converted to more realistic representations as depth 

sections. 

CONCLUSIONS 

Results obtained during the initial test program indi:. 

cate that, with proper design of data acquisition and 

processing procedures, shallow, high-resolution reflection 

seismics can be developed into a useful tool for detailing 

stratigraphic variations between geologically and geophysically logged drill holes located within reasonable distances 

from each other. 

142 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
30. Relation of Selenium at Kesterson National 

Wildlife Refuge to Potential Soil-Forming 

Source Rocks 

By T.S. Presser 

The west side of the San Joaquin Valley of California 

has been identified as an area where selenium has been 

dispersed from soil-forming formations in the California 

Coast Ranges. Because of climate, soil type, presence of 

alluvial clay layers, emplacement of subsurface drains, 

availability of imported irrigation water, type of irrigation, 

and the unique chemical properties of selenium, selenium 

has been biogeochemically cycled. This process has taken 

place throughout geologic time in both the Coast Ranges 

and their alluvial fans and, on a smaller time scale but in a 

more complex way, in the ponds of Kesterson National 

Wildlife Refuge (KNWR), a refuge situated in the valley 

trough. The effects of elevated levels of selenium are seen 

at KNWR in all parts of the ecosystem, including bioaccumulation in the food chain and a 64-percent rate of 

deformity and death in embryos and hatchlings of wild 

aquatic birds (Ohlendorf and others, 1986). Other larger 

areas of wetland habitat in the flood plains of the San 

Joaquin River are also affected, namely the Grassland, 

which encompasses 52,000 acres. Because the pathway of 

agricultural drainage includes the San Joaquin River, the 

San Francisco Bay, and the California Aqueduct, other 

ecosystems and even human health may be affected. 

Studies of the chemical and isotopic relations and 

water and rock reaction data have been completed on water 

samples from the ponds at KNWR, on subsurface agricultural inflows to the San Luis Drain, which is the supply 

canal for the KNWR ponds, and on irrigation supply waters 

in the surrounding area (Presser and Barnes, 1984, 1985). 

For the nine actively inflowing waters to the San Luis Drain 

from the west, Kesterson pond 2, and the San Luis Drain, 

the correlation coefficient of linear regression between 

sodium and sulfate is 0. 99 and between dissolved sulfate 

and selenium is 0. 93. Percent sodium ranged from 55 to 92 

percent of the total cations, and sulfate from 54 to 85 

percent of the total anions present in the waters. The highest 

concentration of sulfate was 22,500 mg/L. Selenium concentrations ranged from 140 to 1,400 ~J.g/L. Selenium was 

found in these waters to be predominantly (up to 98 percent) 

in the form of selenate (Se04 =)where selenium is in the +6 

oxidation state, its highest oxidation state. Care must be 

taken in selection and execution of methodology for analysis because different sensitivities may be exhibited for 

Se +4 and Se + 6 in spectral analysis, and organic selenium 

compounds may be easily volatilized. It was estimated that 

failure to include the reduction step in the hydride generation technique for analysis of selenium in water may 

account for as much as 98 percent of the total selenium 

being left undetected in agricultural drainage water (Presser 

and Barnes, 1984). 

From reaction states in water for various minerals 

(Kharaka and Barnes, 1973), gypsum (CaS04·2H20), mirabilite (Na2S04·10H20), and thenardite (Na2S04 ) were 

found to be associated with waters on the valley floor. 

Gypsum used locally as a soil amendment contained more 

than 0.5 parts per million (ppm) selenium. Thenardite and 

an algal mat from Kesterson pond 1 contained 1. 8 and 13 

ppm selenium, respectively, reflecting both inorganic and 

organic (food chain accumulation) uptake of selenium. 

Thenardite was also identified as a salt crust at the location 

that exhibited the highest concentration of selenium in the 

inflow waters to the San Luis Drain; the salt contained 17 

ppm selenium. These minerals have also been identified in 

the Coast Ranges bordering the western San Joaquin Valley 

in 1977 (Murata, 1977) and more recently in our own 

studies. In both studies, magnesium sulfates and mixed 

sodium and magnesium sulfates were also found. Because 

of the similar chemical and physical properties of sulfur and 

selenium, the inorganic uptake of selenium in these sulfate 

evaporite or efflorescent minerals is now being evaluated as 

part of continuing research on the geologic source of 

selenium. Ground-water and stream chemistry is complex 

in the Coast Ranges and reflects several different regimes 

besides marine sediments; these include ultrabasic intrusive 

rocks, epithermal zones of mercury ore deposition (New 

Idria), and the Franciscan Formation. Potential transport 

mechanisms of selenium include runoff and mass wasting of 

sediment and salts to the valley alluvium, mostly during 

flood events. 

Relation of Selenium at Kesterson National Wildlife Refuge to Potential Soil-Forming Source Rocks 143 
The more insoluble weathering products found in the 

Coast Ranges, limonite, jarosite, and alunite, and minerals 

including pyrite from the cuttings of a 16,000-foot core of 

a well from the alluvium of the west side of the valley in the 

area of concern are also being studied. The amount of 

selenium in these minerals will be quantified. The oxidation 

state of selenium in these minerals as a function of diagenesis and weathering must also be analyzed to evaluate 

mechanisms of inclusion. Solution-precipitation behaviors 

and concentrating mechanisms of these different minerals 

are then, in tum, important in quantitating the major paths 

by which selenium moves. 

The approach to elucidating the source of selenium 

and the mobilization, concentration, and transport mechanisms in the Coast Range formations will also include 

isotopic analysis. Study of the isotopes of water shows 

possible sources and history of the water. Isotopic relations 

of D/H and 180/ 160 in waters in the vicinity of KNWR 

yielded an evaporation trend line whose slope was comparable to those of desert basins. The clustered points for the 

inflow waters to the San Luis Drain, indicating similar 

histories for the waters, fell between the depleted waters of 

the irrigation supply canals and the enriched waters of the 

KNWR ponds with a correlation coefficient of 0.99. 

Ultimately, isotopic studies of source formations can 

be diagnostic and confirmatory of selenium sources and 

sinks and the path by which selenium moves into the ground 

water. The isotopes of both strontium (

87Sr/ 86Sr) and 

selenium (

82Se/ 76Se) are possible candidates for this tracer 

work. Methodology and data for strontium ratios in rocks 

are available (Faure and Powell, 1972); fewer data exist for 

ratios in waters (Stettler and Allegre, 1978). Relations of 

selenium concentrations and strontium fractionations may 

be seen in source rocks, waters, and alluvial material. 

Methodology for measuring selenium ratios is less well 

tested (Hoefs, 1980, p. 51-52) and is more complex, 

because of the large number of possible oxidation states for 

selenium. Transport of selenium entirely in the saturated 

zone (ground water) versus the unsaturated zone may be 

differentiated by opportunities afforded for fractionation. 

REFERENCES CITED 

Faure, Gunter, and Powell, J.L., 1972, Strontium isotope geology: New York, Springer-Verlag, 188 p. 

Hoefs, Jochen, 1980, Stable isotope geochemistry (2d ed.): New 

York, Springer-Verlag, 208 p. 

Kharaka, Y.K., and Barnes, Ivan, 1973, SOLMNEQ-Solutionmineral equilibrium computations: Springfield, Va., 

National Technical Information Service Report 

PB-215-899, 81 p. 

Murata, K.L., 1977, Occurrence of bioedite and related minerals 

in marine shale of Diablo and Templor Ranges, California: 

U.S. Geological Survey Journal of Research, v. 5, no. 5, 

p. 637-642. 

Ohlendorf, H.M., Hothem, R.L., Bunck, C.M., Aldrich, T.W., 

and Moore, J.F., 1986, Relationships between selenium 

concentrations and avian reproduction: North American 

Wildlife Natural Resources Conference Transactions, 

v. 51' p. 330-342. 

Presser, T.S., and Barnes, Ivan, 1984, Selenium concentrations in 

water tributary to and in the vicinity of Kesterson National 

Wildlife Refuge, Fresno and Merced Counties, California: 

U.S. Geological Survey Water Resources Investigations 

Report 84-4122, 26 p. 

---1985, Dissolved constituents including selenium in waters 

in the vicinity of Kesterson National Wildlife Refuge and 

the West Grassland, Fresno and Merced Counties, California: U.S. Geological Survey Water Resources Investigations Report 85--4220, 73 p. 

Stettler, A., and Allegre, C.J., 1978, 87Rb-87Sr studies of waters 

in a geothermal area-The Cantal, France: Earth and 

Planetary Science Letters, v. 38, no. 2, p. 364-372. 

144 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
31. Heavy-Metal Accumulations in Sediments of 

Boston Harbor, Massachusetts 

By Michael H. Bothner 

Boston Harbor, Mass., is a prime example of an 

urban estuary in which environmental conditions have 

seriously deteriorated as a result of industrial and domestic 

waste discharge. In recent years, large areas of the harbor 

have had to be closed to shellfishing. In addition, a large 

number of winter flounder from the harbor have been found 

to have some type of liver cancer (Murchelano and Wolke, 

1985). Recent legislation will eliminate Boston's two antiquated p~imary sewage treatment plants and the scattered 

storm drains that carry untreated wastes during periods of 

high runoff. A secondary sewage treatment plant, targeted 

for completion by the year 2002, is designed for ocean 

discharge of treated liquids and a land-based disposal of 

solid wastes. 

Heavy metals represent one class of contaminants 

present in high concentration in the effluent discharged into 

Boston Harbor. The wastes discharged by the two operating 

sewage-treatment plants are the largest source of metals and 

sediments emptied into the harbor. These discharges have 

resulted in a significant increase in metal concentration in 

sediments, compared with average crustal abundances and 

with clays deposited before the industrial revolution (fig. 

31.1). Profiles of metal concentration in sediment cores 

show a dramatic increase from background levels in buried 

sediments of preindustrial age to concentrations as much as 

20 times higher than background in surface sediments (fig. 

31.2). The elevated concentrations of heavy metals in 

sediments have been used to identify areas of the harbor 

where wastes accumulate. 

We have made some preliminary attempts to interpret 

the history of metal deposition on the basis of 210Pb dating, 

supplemented, in a few cores, by 137Cs analysis. At most 

locations in the harbor, the radioisotope profiles in sediment 

cores suggest that the sediments are being mixed by 

biological and (or) physical processes that complicate the 

determination of accumulation rates. At one location in 

Hingham Bay, however, profiles of both isotopes suggest 

that sediments have been accumulating at a rate of about 2 

cm/yr for approximately the last 70 years (fig. 31.3). 

The limited data indicate that the recent rates of 

sediment accumulation are much faster than the rates one 

would predict from the thickness of unconsolidated sediments deposited since sea level rose following the last 

glacial period. Faster rates during the last century may 

reflect the increasing load of solid wastes discharged to the 

harbor, the increased biological scavenging of suspended 

particulate matter stimulated by additional nutrients, and the 

extensive engineering projects in and around the harbor 

(Fitzgerald, 1980). 

Participants at a symposium that reviewed the marine 

research conducted in Boston Harbor (Kaufman, 1985) 

identified a critical need for a much better understanding of 

the oceanographic processes in Boston Harbor and Bay. A 

comprehensive monitoring program that includes all the 

subdisciplines of oceanography, tailored to the specific 

needs and problems of Boston Harbor, is being discussed by 

the symposium coordinators. 

This program should address the following geochemical questions, which pertain to toxic organic compounds, 

as well as to metals: ( 1) Where and at what rate are waste 

discharges accumulating? (2) How are contaminants partitioned among surficial sediments, mobile suspended particulates, and dissolved phases? (3) What are the transport 

pathways and fate of contaminants added to the system? (4) 

What is the concentration of contaminants in interstitial 

waters, and can contaminated sediments continue to be a 

source of metals and toxic organic compounds after the 

primary sources are reduced or eliminated? (5) What is the 

rate of sediment accumulation in areas that are strongly 

influenced by bioturbation? (6) Which meteorological or 

oceanographic events are responsible for redistributing 

contaminated sediments, and can redistribution by any 

process have an adverse impact on the living resources of 

the harbor? 

There is the capability in the U.S. Geological Survey 

for studies that can be an important supplement to both 

environmental geochemistry and to any comprehensive 

monitoring program initiated in Boston Harbor or in any 

other estuary. These studies include ( 1) synoptic time-series 

measurements to determine the flow regime and sediment 

transport (Butman and others, 1979); (2) seismic-reflection 

and sidescan-sonar profiling to define the shallow sedimenHeavy-Metal Accumulations in Sediments of Boston Harbor, Massachusetts 145 
30 1100 

530 

Ba Cd Cr 

Figure 31.1. Relative concentrations (in parts per million 

(ppm)) of metal in digested sewage sludge from the 

treatment plant in Boston, Mass. (diagonal pattern), average concentration in the upper 2 em of sediment (dots), 

concentration in average crustal rocks (no pattern) 

tary framework and long-term sedimentary processes that 

have operated in estuaries (Knebel and others, 1981; Knebel 

and Scanlon, 1985); and (3) geotechnical studies of estua1400 650 1.3 

Cu Pb Hg 

(Krauskopf, 1967), and concentration in clay (dashes) collected approximately 2 m below sediment surface in 

Boston Harbor. Barium is a metal not used by industry in 

the Boston area. 

rine sediments that can contribute critical information on the 

erodability of sediments and for the siting of pipelines and 

offshore structures (Booth and others, 1984). 

146 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
::r: 

t 

L.U 

0 

0 100 200 300 0 o----, if 

\ 0 

~0 

/ 

I 

0/0 

I 

I 

0 

! 

Cr 

METALS (PPM) 

100 0 100 200 300 

v~ 71 I 

\ I 0 0 

" 0 "'-o I I 0 0 \ 0 ~ 

I ~ 

0 

I 0 

I 0 

I I 

Cu Pb 

Figure 31.2. Profiles of metal concentration plotted 

against sediment depth in a core collected from Hingham 

Bay in Boston Harbor, Mass. 

B 

Figure 31.3. B, Fallout record for 137Cs measured in New 

York City between 1954 and 1978. The preservation of the 

fallout peak in the sediments suggests that biological 

mixing of the sediments is not severe at this location and 

that the sedimentation rate is about 2 cm/yr in agreement 

with estimates derived from the profiles of 210Pb. 

137Cs (DPM/G) 

.2 .3 .4 .5 .6 

10 0 

20 0_ 

- E -0-

u 

~ 30 "0-....... r- 0 0.. 

L.U "\ 0 

-----0-/ 

40 --- --

A 

Figure 31.3. A, Profile of 137Cs activity plotted against 

sediment depth in a core collected from Hingham Bay in 

Boston Harbor, Mass. 

0 0 

c 

Figure 31.3. C, Profile of excess 210Pb with sediment depth 

(same location as core in figure 31.3A). If sediment mixing 

is assumed to be minor and restricted to the upper 10 em 

of sediment, the average is about 2 em/yr. DPM/G, disintegration per minute per gram. 

Heavy-Metal Accumulations in Sediments of Boston Harbor, Massachusetts 147 
REFERENCES CITED 

Booth, J.S., Silva, A.J., and Jordan, S.A., 1984, Slope-stability 

analysis and creep susceptibility of Quaternary sediments 

on the northeastern U.S. Continental Slope, in Denness, 

Bruce, ed., Seabed mechanics: London, Graham and Trotman Limited, p. 65-75. 

Butman, Bradford, Noble, M.A., and Folger, D.W., 1979, 

Long-term observations of bottom current and bottom 

sediment movement on the mid-Atlantic continental shelf: 

Journal of Geophysical Research, v. 84, no. C3, 

p. 1187-1205. 

Fitzgerald, M.G., 1980, Anthropogenic influence of the sedimentary regime of an urban estuary-Boston Harbor: Woods 

Hole, Mass., Woods Hole Oceanographic Institution, 

unpublished Ph.D. dissertation, 298 p. 

Kaufman, J.R., convener, 1985, Science and policy of Boston 

Harbor and Massachusetts Bay-Planning for the twentyfirst century: Boston, Mass., Massachusetts Bay Marine 

Studies Consortium [no page numbers]. 

Knebel, H.J., Martin, E.A., Glenn, J.L., and Needell, S.W., 

1981, Sedimentary framework of the Potomac River estuary, Maryland: Geological Society of America Bulletin, 

v. 92, no. 8, p. 578-589. 

Knebel, H.J., and Scanlon, K.M., 1985, Sedimentary framework 

of Penobscot Bay, Maine: Marine Geology, v. 65, 

p. 305-324. 

Krauskopf, K.B., 1967, Introduction to geochemistry: New York, 

McGraw-Hill, 721 p. 

Murchelano, R.A., and Wolke, R.E., 1985, Epizootic carcinoma 

in the winter flounder: Science, v. 228, p. 587-589. 

148 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
32. New Bedford Harbor and Buzzards BayTransport of Pollutants on Fine-Grained Marine 

Sediments 

By Bradford Butman 

The transport of fine-grained sediment particles in the 

coastal ocean is a major factor in determining the long-term 

fate of pollutants introduced into the marine environment 

(such as polychlorinated biphenyls (PCB 's), heavy metals, 

and polyaromatic hydrocarbons, and so on), which are 

strongly adsorbed by these particles. Transport of particles 

is determined by the physical characteristics of the material 

(size, density, shape, and settling velocity), by the spatial 

and temporal distribution of currents strong enough to 

resuspend the particles or weak enough to allow them to 

settle, by the circulation patterns that carry the suspended 

particles, and by biological processes that can mix the 

sediments on the sea bed and can alter the physical 

characteristics of the sediment by reworking or binding the 

particles. The distribution of sediments in the marine 

environment is the long-term result of these physical and 

biological processes. 

Buzzards Bay, a semi enclosed coastal bay about 40 

km long and 15 km wide, is located along the southern 

Massachusetts coast (fig. 32.1). The bay is open to Rhode 

Island Sound to the southwest and to Vineyard Sound to the 

south and southeast through several small passages between 

the Elizabeth Islands. The water is 20 m deep near the 

mouth of the bay and gradually shoals to less than 5 m deep 

at the head. The bottom sediment distribution in the bay is 

complex and reflects the glacial history of the area, as well 

as modem physical processes (Moore, 1963; Robb and 

Oldale, 1977). Fine-grained silt and clay are found along 

the axis in the deeper part of the bay, and mixtures of sand, 

silt, and gravel are distributed around the perimeter of the 

bay and near the mouth where the topography is more 

rugged. 

New Bedford Harbor is located along the western 

shore of Buzzards Bay in the Acushnet River estuary (fig. 

32.1). Between about 1950 and 1970, two manufacturing 

firms discharged large quantities of PCB's to New Bedford 

Harbor. As a result, sediments in the inner harbor are 

heavily contaminated with PCB 's (Farrington and others, 

1985); concentrations in the surficial sediments are as high 

as 1,250 parts per million (ppm), and concentrations in 

commercial fish species are as high as 26 ppm (the Food 

and Drug Administration's limit for human consumption is 

5 ppm). Mussels analyzed as part of the Environmental 

Protection Agency's (EPA) Mussel Watch program contained PCB' s in concentrations as high as 49 ppm, at least 

50 times higher than concentrations found at other urban 

East Coast locations and 1,000 times higher than those 

found at pristine locations (Farrington and others, 1985). 

Although there is only a limited exchange of water and 

particles through the hurricane barrier at the mouth of the 

harbor (see fig. 32.1), PCB' s are found in the sediments and 

water column and in organisms in Buzzards Bay near New 

Bedford. Typical concentrations are 0.1-1.0 ppm in the 

sediments and 1-10 parts per trillion in unfiltered water. 

Inner New Bedford Harbor is closed to all fishing, and 

portions of the outer harbor and Buzzards Bay are also 

closed to certain fisheries (fig. 32.1). New Bedford Harbor 

was declared an EPA Superfund site in 1982. 

The long-term fate of PCB' s is partially determined 

by the physical and biological processes that transport water 

and fine-grained sediments from the inner harbor to Buzzards Bay and throughout the bay. The currents in the bay 

can be conceptually separated into a seasonal flow, lowfrequency currents driven by wind and the density field, 

tidal currents, and high-frequency currents associated with 

surface and internal waves. Preliminary analysis of pilot 

field measurements made by investigators at the U.S. 

Geological Survey (USGS) and the Woods Hole Oceanographic Institution by using specialized near-bottom instruments (fig. 32.2) (Butman and Folger, 1979; Williams, 

1985), current meters, and other techniques provides some 

information on these currents, illustrates their temporal and 

spatial variability, and identifies some of the important 

processes causing sediment transport in the bay (Signell, 

1987; Rosenfeld and others, 1984). The observations suggest a complex residual flow pattern composed of small 

circulation cells that may be partially driven by the tidal 

circulation. Net near-bottom current speeds associated with 

New Bedford Harbor and Buzzards Bay-Transport of Pollutants on Fine-Grained Marine Sediments 149 
71°00• 

• USGS 

e WHOI 

'\~ 

-....::=---10 ~ <¢ ~ £,. \.. \1. OL..-~_._ ............ ___._5.__~_._ ............ ___.__,10 KILOMETERS 

Figure 32.1. Buzzards Bay, Mass., showing locations 

where current or near-bottom sediment movement 

observations have been made. The measurements by 

the U.S. Geological Survey (USGS) were made at 

stations 1, 3, 7, 8, and 9 during 1984-85. Regions 

closed to fishing activity because of polychlorinated 

biphenyl (PCB) contamination are Area I (closed to all 

0 5 NAUTICAL MILES 

CONTOURS IN METERS 

fishing, shellfishing, and lobstering), Area II (closed 

to bottom-feeding finfishing and lobstering), and 

Area Ill (closed to lobstering). The highest levels of 

PCB's are found near New Bedford to the north of the 

Hurricane Barrier. Adapted from Robb and Oldale 

(1977) and from National Ocean Survey chart 13230. 

WHOI, Woods Hole Oceanographic Institution. 

150 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
- --- .... 

Figure 32.2. Bottom tripod system designed for studies of 

near-bottom sediment transport. The system measures 

current, temperature , light transmission, and pressure 

and photographs the sea floor. The instruments have been 

used extensively on the continental shelf to document 

processes of sediment transport. A, current sensor; B, 

pressure sensor; C, transmissometer; D, camera; E, camera strobe; F, camera battery; G, data logger; H, battery 

pack; I, acoustic release;), rope canister; and K, recovery 

float. 

this residual circulation are on the order of 1-5 cm/s, and 

water-particle displacements are on the order of 1-5 km/d; 

thus, particles transported with the residual flow can travel 

across the bay in a few days. The tidal currents are 

dominated by the M2 (semidiumal, period of 12.42 hours) 

tide; their speed is about 25 cm/s near the mouth of the bay 

and decreases to less than lO cm/s near the head. Neither the 

residual circulation nor the tidal currents are strong enough 

to resuspend the existing sediments by themselves, except 

perhaps during spring tides near the bay mouth . However, 

intense near-bottom sediment resuspension and transport do 

take place during strong storms (fig. 32.3). During these 

storms, oscillatory currents associated with surface waves 

are primarily responsible for increasing the bottom stress 

above the critical value for sediment resuspension (see 

Grant and Madsen, 1979, and Butman, 1987, for a description of the effect of surface waves on bottom stress). Once 

resuspended, the sediments are transported in the direction 

of the wind-driven currents. At least for the central part of 

the bay, the near-bottom currents during intense storms 

flow opposite to the wind. A working hypothesis is that the 

storm-driven flows will distribute fine-grained sediments to 

the central part of the bay; escape from Buzzards Bay to 

Rhode Island Sound may occur only during strong winds 

from the southwest when waves are large because of the 

long fetch and net near-bottom flow is opposite to the wind 

(out of the bay). These observations on sediment transport 

are typical of other coastal areas where sediment movement 

is episodic and the net transport is the cumulative result of 

many transport events. 

The transport of PCB 's in Buzzards Bay is just one 

example where a detailed understanding of the dynamics of 

particulate transport in the coastal ocean is important in 

assessing the long-term effects from localized pollutant 

sources and in devising remedial strategies for cleanup. 

Discharge of sewage effluent and sludge (for example, into 

Boston Harbor; see Bothner, this volume) and dumping of 

dredge spoil or drilling muds into coastal waters are other 

examples. Important problems occur nearshore in coastal 

bays and estuaries, as well as offshore on the continental 

shelf and slope. Scientists in the USGS have already 

conducted extensive field studies of sediment transport 

along the U.S. East- and West-Coast continental margins 

(Drake and Cacchione, 1985; Butman, 1987; Bothner, this 

volume). 

Studies to investigate the transport of fine-grained 

material provide an excellent opportunity to conduct sound 

research that has direct practical benefit. Comprehensive 

studies of particulate transport in the coastal zone should be 

multidisciplinary and include (1) geologic site characterization (bathymetry, high-resolution and side-scan sonar surveys, surficial sediment texture); (2) geochemistry (pollutant characterization, distribution between dissolved and 

particulate phases, sediment accumulation rates, mixing 

rates); (3) circulation and sediment transport (advection, 

resuspension, deposition); (4) biological processes in the 

water column and on the sea floor that affect particulate 

transport (mixing, repackaging, binding) and chemical 

composition. The mix of these various study components 

appropriate to a given area will depend on the particular 

transport problem. Scientists within the USGS are uniquely 

qualified to address these program components. 

ACKNOWLEDGMENTS 

R. Signell , C.A. Butman, W.D. Grant, R.C. Beardsley, and L. Rosenfeld at the Woods Hole Oceanographic 

Institution contributed to the research and ideas presented 

here. 

New Bedford Harbor and Buzzards Bay-Transport of Pollutants on Fine-Grained Marine Sediments 151 
A 

Buzzards Bay 

~~~ 1 6 11 16 21 26 ~~~ 1 6 11 16 21 NOV DEC 

1984 

:; : [Beo~~tteooot;oo 

0 I ; ; ; I : :' 

Sta. 8 

J 

6 

4::::;: 

1 6 11 16 

~--:~:·:::~::::- 21 26 1 6 11 16 21 NOV DEC 

1984 

:;~bm Attenuation 

~-: ___,~......__::-:~0 

~::; 6 11

1 16 21 26 1 6 11 16 21 

Sta. 7 

1 NOV 

1984 :; ~I Beam 

Attenuation 

1 6 

-;; 

11 NOV 

1984 

8 PSDEV 

6 

§)4 

Sta. 1 

DEC 

Sta. 

~~~-.._.____;~--~:--; 16 21 26 1 6 11 16 

DEC 

8 

6 

4 g) 

2 2 

0 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ 0 

1 6 11 16 21 26 1 6 11 16 21 NOV DEC 

1984 

~ : I New Bedfo'd W.od st'e" I I :a 

~ ~~l~ L..,t.. bJ.J.tW!l..;,... .. M! v.J ~ ~ 

350 

. 270 0 

~180 

ci 

~ 90 

1 6 11 16 21 26 1 6 11 16 21 NOV DEC 

1984 

Direction 

0 ~~~~~~~~~~~~~--~~~~~~~~~~~~~~~~~~~ 

1 NOV 

1984 

6 11 16 21 26 1 

DEC 6 11 16 21 

350 

270 . 

0 

w 1800 

ci 90~ 

0 

152 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Buzzards Bay 

6 PSDEV 

5 

4 

~3 

2 

Station 8 

6 

5 

4 

3~ 

2 

0 ~~~~~~~--~~~~~~~~~~~~~~~~~~~~~~~0 

~ 

1 6 1 1 16 21 26 1 6 11 16 21 NOV DEC 

1984 

3.0 Beam Attenuation 

2.5 

2.0 

........ 1.5 

3.0 

2.5 

2.0 

~ 

1.5 ........... 

1.0 

0.5 

1.0 

0.5 

0.0 ~----~~~~~~~~~~~~~~~~~~~~~--~-r~~--~~~~~~~~ 0.0 

1 6 NOV 

1984 

35 Speed 

30 

25 

~20 

~15 

10 

5 

11 16 21 26 1 DEC 6 11 16 21 

35 

30 

25 

20~ 

~ 

1 5u 

10 

5 

0 ~--~~~~~~~~~~~~~~~~~~~~~~~~-r~~--~~~~~~~~ 0 

1 NOV 

1984 

6 11 

6 Low-passed Current 

4 

2 (/) 

~0 u 

-2 

-4 

16 21 26 1 DEC 6 11 16 21 

6 

-6~--~~~~~~~~~~~~~~~~--~~--~--~~-r~~~~~~~~~~~ -6 

1 6 11 16 21 26 1 6 11 16 21 NOV DEC 

1984 

B 

Figure 32.3. A, Beam attenuation (proportional to suspended sediment concentration) at stations 1, 7, and 8; 

near-bottom pressure fluctuations (PSDEV) at stations 1 

and 8 (a rough measure of the amp I itude of the waves near 

the bottom); and wind stress and direction at New Bedford, Mass., from November 1 to December 20, 1984. The 

observations clearly show the episodic resuspension of 

near-bottom sediments associated with waves, especially 

on December 8. B, Near-bottom wave fluctuations, beam 

attenuation 2 m above bottom, current speed 1 m above 

bottom, and low-passed current at station 8. The lowpassed "stick" diagram shows the direction of the daily 

averaged flow (oscillatory tidal currents are removed). The 

current sticks originate along the time axis and point in the 

direction of net flow. MB, millibars; 1/M, inverse of 

meters; ANG. DEG., angles of degrees; CM2, cm2 • 

New Bedford Harbor and Buzzards Bay-Transport of Pollutants on Fine-Grained Marine Sediments 153 
REFERENCES CITED 

Butman, Bradford, 1987, Physical processes causing surficialsediment movement, chap. 13, in Backus, R.H., ed., 

Georges Bank: Cambridge, Mass., M.I.T. Press, 

p. 147-162. 

Butman, Bradford, and Folger, D.W., 1979, An instrument 

system for long-term sediment transport studies on the 

continental shelf: Journal of Geophysical Research, v. 84, 

no. 23, p. 1215-1220. 

Drake, D.E., and Cacchione, D.A., 1985, Seasonal variation in 

sediment transport on the Russian River shelf, California: 

Continental Shelf Research, v. 4, p. 495-514. 

Farrington, J.W., Tripp, B.W., Davis, A.C., and Sulanowski, J., 

1985, One view of the role of scientific information in the 

solution of enviro-economic problems, in Chao, N .L., and 

Kirby-Smith, William, eds., Proceedings of the International Symposium on Utilization of Coastal Ecosystems, 

Planning, Pollution, and Productivity, Nov. 21-27, 1982, 

Rio Grande, Brazil: Rio Grande, RS, Brazil, Edition da 

FURG, p. 73-102. 

Grant, W.D., and Madsen, O.S., 1979, Combined wave and 

current interaction with a rough bottom: Journal of Geophysical Research, v. 84, p. 1797-1808. 

Moore, J.R., Ill. 1963, Bottom sediment studies, Buzzards Bay, 

Massachusetts: Journal of Sedimentary Petrology, v. 33, 

no. 3, p. 511-558. 

Robb, J.M., and Oldale, R.N., 1977, Preliminary geologic maps, 

Buzzards Bay, Massachusetts: U.S. Geological Survey 

Miscellaneous Field Studies Map MF-889, 2 sheets. 

Rosenfeld, L.K., Signell, R.P., and Gawarkiewicz, G.G., 1984, 

Hydrographic study of Buzzards Bay, 1982-83: Woods 

Hole Oceanographic Institution Technical Report 

WHOI-84-5, 134 p. 

Signell, R.P., 1987, Tide- and wind-forced currents in Buzzard's 

Bay, Massachusetts: Woods Hole Oceanographic Institution Technical Report WHOI-87-15, 86 p. 

Summerhayes, C.P., Ellis, J.P., Stoffer, P., Briggs, S., and 

Fitzgerald, M.J., 1977, Fine-grained sediment and industrial waste distribution and dispersal in New Bedford 

Harbor and western Buzzards Bay, Massachusetts: Woods 

Hole Oceanographic Institution Technical Report 

WHOI-76-115, 110 p. 

Williams, A.J., III, 1985, BASS, an acoustic current meter array 

for benthic flow-field measurements, in Nowell, A.R.M., 

and Hollister, C.D., eds., Deep ocean sediment transport: 

New York, Elsevier, p. 345-355. 

154 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
33. The Georges Bank Monitoring ProgramTrace Metals in Bottom Sediments 

By Michael H. Bothner 

Exploratory drilling for petroleum resources in the 

rich fishing grounds off New England has always been 

controversial. When the plans for lease sale 42 (Georges 

Bank) were made known during the mid 1970's, a legal 

battle was initiated by fishing and environmental groups 

against the U.S. Department of Interior. Part of the settlement of this controversy was the creation of a Biological 

Task Force for Georges Bank, which had the responsibility 

of designing a monitoring program that would evaluate the 

environmental effects of offshore drilling and provide an 

early warning of adverse effects. 

Part of the monitoring program was designed to 

establish the concentration of trace metals in sediments 

prior to drilling on Georges Bank and to monitor the 

changes in concentrations that could be attributed to exploration activities. Some of the specific questions addressed in 

this study were ( 1) Where do discharged drilling muds 

accumulate on Georges Bank? (2) How great an increase in 

trace metals results from accumulation of drilling mud? and 

(3) In areas where drilling-mud components accumulate, 

how long do they remain at an elevated concentration after 

the drilling is completed? Details of this study and the 

results of the other studies conducted as part of this 

comprehensive monitoring program are published elsewhere (Michael and others, 1983; Maciolek-Blake and 

others, 1985; Bothner and others, 1986; Phillips and others, 

1987). 

The first cruise of the monitoring program took place 

just before exploratory drilling commenced in July 1981, 

and subsequent cruises were conducted on a seasonal basis 

over a 3-year period. Samples were collected at regional 

stations 1-18 (fig. 33.1) and at 29 site-specific stations (fig. 

33.2) centered around a drilling site. 

The mean current flow on the southern flank of 

Georges Bank is to the southwest, parallel to depth contours, although the mean current can reverse in direction in 

response to storm winds or other oceanographic events 

(Butman and others, 1982). With respect to the mean 

current flow, transect 1 to the east is upstream, and transect 

3 is downstream of the blocks offered in lease sale 42. 

The chemistry samples were collected by means of a 

teflon-coated grab sampler. The upper 0-2 em of sediment 

was analyzed for 12 trace metals. The only metal that 

showed a change in concentration as a result of drilling was 

barium. Barium is added to drilling mud in the form of the 

mineral barite (BaS04). 

The barium concentrations in sediments at most 

stations within the site-specific survey (fig. 33 .3) increased 

after the drilling began, just before cruise 3, and reached a 

maximum at the time of cruise 5, just after drilling was 

completed. Concentrations then decreased in the period 

following drilling. The maximum increase in the concentration of barium in bulk sediments (undifferentiated with 

respect to size) was from about 30 parts per million (ppm) 

to 132 ppm adjacent to this drilling rig and to 172 ppm next 

to the drill rig at station 16. 

The detailed sampling and analysis have provided an 

opportunity to address a number of questions about the fate 

of drilling mud specifically and the fate of other pollutants 

in general that may be discharged on Georges Bank: ( 1) 

Where does it go? (2) How is it transported? and (3) How 

long does it persist near the site of deposition? 

Increases in the concentration of barium in the bulk 

sediment were found 6 km away from the drill rig near 

station 5 (fig. 33.3) but were not observed at regional 

stations more distant from drilling locations. However, by 

analyzing the fine fraction (silt and clay) of the sediment for 

barium, we greatly increased our ability to detect small 

increases in barium. Within the fine fraction, we observed 

increases in barium concentration at stations 10 and 12 

approximately 65 km west of drilling. We also measured an 

increase at stations 2 and 3, 35 km east of the easternmost 

drilling location, possibly in response to a reversal in mean 

current flow. 

How is barium transported? We deployed sediment 

traps near the drill site after drilling was completed and 

caught material rich in barium. The spatial arrangement of 

the traps and the barium concentrations suggested that some 

of the drilling mud initially deposited near station 5-1 (fig. 

33.3) was being resuspended by tidal and storm currents 

The Georges Bank Monitoring Program-Trace Metals in Bottom Sediments 155 
EXPLANATION 

I Transect 

c:!J Lease Sale 42 Tracts (Sold) 

0 25 50 miles 

0 25 50 i:::ocz=-::O"""'=.....t kilometWII 

Botllrmetrr 111 meters 

sa• 

Figure 33.1. Regional sampling station array, Georges Bank. Site-specific array in block 312 is centered at station 5. 

Stations 15-21 sampled only once during this program. From Bothner and others (1986). 

CROSS-SHELF 

.IlEA# t't/RREIY7 

23 

24 

t 

-IM.ItJR Al'l.> 

7/lJA! Ct/RK#7 R!I,O.>E 

l 

SITE SPECIFIC SAMPLING PLAN 

and was carried in the water column. Transport of this 

material along the surface of the sea floor was probably 

taking place also. 

How fast is the drilling-related barium removed from 

the surface sediments by natural processes? We computed 

an inventory of barite in the upper 2 em of sediment by 

using the closely spaced stations within the 0.5- to 2-km 

annulus of the site-specific survey. The station closest to the 

drill site was excluded because of high spatial variability. 

By cruise 3, just after drilling began, the inventory of barite 

had increased from a background level of about 50,000 

pounds and continued to increase until it reached a maximum of about 90,000 pounds just after drilling was 

<IIIII Figure 33.2. Site-specific sampling station array around 

regional station 5 (block 312), Georges Bank. Stations 

5-7, 5-13, 5-15, 5-17, 5-19, 5-21, 5-23, 5-24, 5-26, and 

5-27 are secondary stations (of lower priority) and have 

not been analyzed routinely. From Bothner and others 

(1986). 

156 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
"'200b·8 

8::100 ~ 

....... I '--......--.-. 

CRUISE 2 4 6 8 10 12 

200

b·f8 100 

.._.......... ... -...--.-. 

200c·/4 

100 

.__..........__ 

2 4 6 8 10 12 24681012 

t~~ 

I~ :r.A--::: j~M =r~ 200

L·28 100 

........_...... .... r' ........ 

2 4 6 8 10 12 2 4 6 8 10 12 2 4 6 8 10 12 2 4 6 8 10 12 2 4 6 8 10 12 

5·29 ~ ~~~H~ ~ ~ +················· ---------- +-- ----+-·· -+- -- -+----+----+-- ---- ---+·----------------------------·------ ······+ 

6km WEST 2 I 0.5 DRill 0.5 I 2 6 km EAST 

SITE 

JHO 200 5·12 I k/~UTH J5-6 

~ 2 4 6 8 10 12 100 /. ~ 2 4 6 8 10 12 .... ~· \_., ____ 2 4 6 8 10 12 

Figure 33.3. Concentrations in parts per million (ppm) of 

barium (circles) in bulk sedjment on different sampling 

occasions near the drill site at block 312, Georges Bank. 

Stations are located on east-west and north-south 

transects through the drill site (see figure 33.2). Drilling 

completed (cruise 5). The barium level then decreased to 

about 10 percent of the background by the end of the 

program (fig. 33.4). Replotting the net inventory (total 

minus ~ackground, fig. 33.5) on a semilog plot yields two 

straight lines from which half-lives can be calculated. For 

the first year following drilling, the removal half-life is 0.34 

year; for the second year, it is 3.4 years. The slower rate for 

the second year may indicate that residual barite is coarser 

and (or) more deeply buried and transported only by more 

energetic storms, which are less frequent. 

The rates of barium dispersal at station 5, located at 

80-m water depth, are probably representative of the rates in 

other areas of the bank at comparable water depth. The rates 

may be faster in shallower water or slower in deeper water 

in response to the intensity of sediment transport processes 

(Butman, 1987). 

In conclusion, this study has shown that, of the 12 

trace metals analyzed in sediments, only barium increased 

as a result of drilling. The concentrations did not reach 

levels considered to be hazardous to benthic organisms. 

Because of the low toxicity of barium in the form of barite 

(BaS04), no adverse chemical stress to bottom-dwelling 

organisms is expected from the measured increases in 

barium concentrations. However, there is little information 

began after the second cruise and ended just before the 

fifth cruise. Error bars are one standard deviation among 

three individual replicates. ND, no data. From Bothner 

and others (1986). 

TIME, IN YEARS 

• 0 0 .5 1.0 1.5 2.0 2.5 3.0 .... 10 I 

)( 

Cl) /0 c 

::l 

z 8 0\ 0 I "-No..._ D.. 

~ 6 

o o-o--o-o------o 

• o-o..........- 0 

Cl) 

CD 4 a:l 

Cl) 

<( 2 

'i 

::l 

a: 0 I 

<( 2 3 4 5 6 7 8 9 10 11 12 a:l 

CRUISE 

~ ~ N N N N 13 13 C") 

~ ~ ~ ~ ~ 13 ~ ~ 

~ > CD ~ ~ > CD ~ ~ > m w 0 w 0 w 0 w z :l z u.. :i :l z u.. :i :l z u.. .., .., .., :l 

.., 

Figure 33.4. Total inventory of barite (calculated from 

barium concentrations) within the annulus between 0.5 

and 2 km from station 5,. Georges, Bank, on different 

sampling occasions. ND, no data. From Bothner and 

others (1986). 

The Georges Bank Monitoring Program-Trace Metals in Bottom Sediments 157 
0 

(!) 1.0 0 

z 

z 

< 

~ 

w 

a: 

.8 

.6 

0 .4 

en 

co 

co 

LL 

0 

~ .2 

i= 

u 

<( 

a: 

LL 

.1 

5 

N 

~ 

>- ...J 

:::> 

..., 

.33 .52 

6 7 

N C") 

~ ~ 

> Ill 

0 w z u.. 

TIME, IN YEARS 

.81 .97 1.31 1.53 1.86 

0 

8 9 10 11 12 

CRUISE 

C") C") C") 

~ ~ ~ ; ; >- >- > lXI w < ...J 0 w z ~ :::> z u.. ..., :::> 

..., 

Figure 33.5. Decrease of the net barite inventory within 

the annulus between 0.5 and 2 km from station 5, Georges 

Bank, with time. Values are based on analyses of the bulk 

sediments. Fraction remaining is relative to the amount 

present at the time of cruise 5, 4 weeks after drilling was 

completed. From Bothner and others (1986). 

concerning the effects on benthic organisms of long-term 

exposure to low concentrations of drilling mud. The biological studies of benthic organisms conducted as part of 

this monitoring program showed no effects attributable to 

drilling (Maciolek-Blake and others, 1985; Neff and others, 

in press). After drilling was completed, the energetic 

sediment transport processes on Georges Bank resuspended 

the barite from its location close to the drill rig and 

transported it to distances at least 65 km west and 35 km 

east of the drilling locations. These results offer some 

perspective to the fate and effects of other pollutants that 

may be added to Georges Bank in the future. If the pollutant 

is rendered harmless by dilution, then the environmental 

concern is minimized. On the other hand, if the pollutant is 

dangerous at any concentration, then the problem may 

intensify because the same energetic processes will disperse 

the pollutant and quickly endanger a wide area of the bank. 

REFERENCES CITED 

Bothner. M.H .. Rendigs, R.R., Campbell, Esma, Doughten, 

M.W., Parmenter, C.M., O'Dell, C.H., DiLisio, G.P., 

Johnson, R.G., Gillison, J.R., and Rait, Norman, 1986, 

The Georges Bank Monitoring Program 1985-Analysis of 

trace metals in bottom sediments during the third year of 

monitoring: U.S. Geological Survey Circular 988, 60 p. 

Butman, Bradford, 1987, Physical processes causing surficialsediment movement, chap. 13, in Backus, R.H., Georges 

Bank: Cambridge, Mass., M.I.T. Press, p. 147-162. 

Butman, Bradford, Beardsley, R.C., Magnell, B., Frye, D., 

Vermersch, J.A., Schlitz, R., Limeburner, R., Wright, 

W.R., and Noble, M.A., 1982, Recent observations of the 

mean circulation on Georges Bank: Journal of Physical 

Oceanography, v. 12, p. 569-591. 

Maciolek-Blake, Nancy, Grassle, J.F., and Neff, J.M., 1985, 

Georges Bank benthic infauna monitoring program-Final 

report for third year of sampling: Prepared for U.S. 

Department of the Interior, Minerals Management Service, 

contract 14-12-0001-29192. 354 p. and appendixes. 

(Available from Battelle New England Marine Research, 

397 Washington St. , Duxbury, Mass., and Woods Hole 

Oceanographic Institution, Woods Hole, Mass.) 

Michael, A.D., Long, C.D., Maurer, D., and McGrath, R.A., 

1983, Georges Bank benthic infauna historical study: A 

final report submitted to U.S. Department of the Interior, 

Minerals Management Service, contract 14-12-0001-

29190, National Technical Information Service Report 

PB83252114, 171 p. 

Neff, J.M., Bothner, M.H., Maciolek, N.J., and Grassle, J.F., 

1989, Impacts of exploratory drilling for oil and gas on the 

benthic environment of Georges Bank: Marine Environmental Research, v. 27, p. 77-114. 

Phillips, C.R., Payne, J.R., Lambach, J.L., Farmer, G.H., and 

Sims, R.R., Jr., 1987, Georges Bank monitoring program-Hydrocarbons in bottom sediments and hydrocarbons and trace metals in tissues: Marine Environmental 

Research, v. 22, p. 33-74. 

158 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
34. Geochemical Studies of Plants and Soils in the 

Beluga Coal Field, Alaska 

By R.C. Severson and Larry P. Gough 

Evaluation of the geochemistry of undisturbed plants 

and soils is essential for objective predictions of the 

rehabilitation potential of an area to be disturbed by strip 

mining. These data also can be used after mining and 

rehabilitation to monitor geochemical changes in the landscape resulting from the rearrangement of rock strata and 

the disruption of soil development and of natural plant 

communities. 

A predevelopmental geochemical survey was conducted for the Capps area of the Beluga coal field (fig. 34.1; 

table 34.1). Soil and plant collections were conducted 

according to an analysis-of-variance sampling design. This 

design allowed us to ( 1) determine the appropriate scale for 

geochemical mapping, (2) estimate the minimum number of 

0 10 20 30 KILOMETERS 

I I I I 

Figure 34.1. Location of the Capps coal field, Alaska. 

samples necessary to prepare stable map patterns, and (3) 

establish geochemical baselines. The data were also used to 

examine the relations between soil geochemistry and plant 

uptake. Details of the methods used and results obtained are 

given in Severson and Gough ( 1983, 1984) and Gough and 

Severson (1983). A summary of these results is presented 

here. 

Stable geochemical maps were prepared, on the basis 

of mean element content within a 1-km2 cell, for pH and 

total levels of Al, Cu, Fe, Mg, P, Sr, and V and for 

diethylenetriamine pentaacetic acid- (DTPA-) extractable 

levels of Cu, Mn, P, and Zn in surface soil zones. Stable 

geochemical maps were also prepared for plant materials: 

willow (Al, As, B, Ca, Cu, Fe, K, La, Ni, P, S, and Sr) and 

Geochemical Studies of Plants and Soils in the Beluga Coal Field, Alaska 159 
Table 34.1. Observed range in concentration (in parts per million unless otherwise indicated) of six elements in samples 

of two soil zones and three plant species (dry weight basis) from the Capps coal field, Alaska 

[n, number of samples] 

Sample Aluminum Copper Iron Manganese Phosphorus Zinc 

AB-DTPA1 soil extract 

Upper zone (n=90) .................. 19-240 1.9-9.3 160-560 3.8-64 6-60 0.5-8.2 

Lower zone (n=90) .................. 32-760 1.1-15 140-750 0.7-21 7-50 0.5-6.9 

Total content in soil 

Upper zone (n=90) .................. 7.2-10% 22-7 3.8-5.9% 860-1,300 70-110 61-98 

Lower zone (n = 90) .................. 4.0-9.5% 11-120 1.3-18% 220-2,800 30-1,500 30-110 

Calamagrostis 

canadensis (n=26) ................... <16-36 5-15 16-84 200-720 0.16-0.52% 29-72 

Festuca altaica (n=64) ................. <16-400 3.1-13 16-260 170-690 0.19-0.45% 4.7-80 

Salix pulchra (n=90) ................... 16-220 2.1-12 16-130 52-340 0.072-0.33% 48-120 

1 AB-DTPA, ammonium bicarbonate-diethylenetriamine pentaacetic acid. 

grass (As, B, Ba, Ca, Cu, Mg, Na, and S). The map 

patterns suggest relative independence of soil geochemistry 

to that of the plants; however, DTPA-extractable soilelement levels correspond better with plant chemistry than 

do total soil-element levels. Geochemical baseline data for 

soils and plants suggest that these compositions are not 

unusual when compared with geochemical baseline data 

from other natural areas. 

Table 34.1 lists the observed range in concentration 

of six biologically important elements as determined in a 

soil extract, in a total digestion of soil, and in the dry 

material of three plant species. The extractable and total 

concentrations measured in the soil are assumed to represent 

physiologically acceptable ranges within which the normal 

growth of these three species takes place. These soilconcentration ranges, therefore, may be used in judging the 

feasibility of revegetating areas disturbed by mining and 

similar operations when native vegetation is to be used in 

site rehabilitation. The range of element concentrations in 

plant materials is also a measure of physiological tolerance. 

Additional work is needed, however, to determine if soilextractable levels are a good measure of element availability 

for the uptake and translocation of these elements in these 

plants. 

REFERENCES CITED 

Gough, L.P., and Severson, R.C., 1983, Chemical analyses of 

native soil and vegetation samples, Capps coal field, 

Alaska: U.S. Geological Survey Open-File Report 83-246, 

58 p. 

Severson, R.C., and Gough, L.P., 1983, Chemical composition 

and variability of soils from the Capps coal field, Alaska: 

U.S. Geological Survey Open-File Report 83-190, 39 p. 

---1984, Estimated physiological tolerance ranges for 

selected elements in soils, Capps coal field, in Reed, K.M., 

and Bartsch-Winkler, Susan, eds., The United States Geological Survey in Alaska-Accomplishments during 1982: 

U.S. Geological Survey Circular 939, p. 75-78. 

160 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
35. Potential Saltwater Intrusion into Freshwater 

Aquifers During Exploration for and Mining of 

Phosphorite off the Southeastern United States 

By Frank T. Manheim 

Studies in the 1980's (Riggs, 1984) demonstrated the 

seaward extension of major phosphorite resources off the 

North Carolina coast in Onslow Bay; similar extensions off 

South Carolina, Georgia, and Florida are possible. Evaluation and development of this resource present a possible 

hazard to freshwater aquifers. 

New slurry mining technology promises to extend 

mining of phosphorite to depths as great as 100 m beneath 

the sea floor. On the basis of current stratigraphic information and the new technology, some experts predict that the 

Atlantic margin from North Carolina to Florida will prove 

to contain the largest mineable phosphorite resource in the 

world. The new slurry mining technique not only permits 

mining of deeper deposits but also permits tailings and other 

wastes to be deposited within the caverns that are left after 

the ore is recovered. The technique creates less turbidity 

and fewer other environmental effects than do alternative 

mining methods, such as dredging. The possibility of 

offshore mining may be enhanced by the fact that the 

opening of new mines in the Florida phosphate fields has 

virtually ceased as a result of environmental or local 

opposition. 

Exploration drilling and drilling associated with the 

phosphorite development will result in invasion by seawater 

of buried deposits that are the seaward extension of freshwater aquifers. This invasion may adversely affect offshore 

freshwater-bearing strata that serve as buffer zones against 

saline-water encroachment into land aquifers. These 

freshwater-bearing offshore strata first became known in the 

late 1960's as a result of the Joint Oceanographic Institutions Deep Earth Sampling Project (JOIDES) drilling off 

Florida. Studies showed that fresh and brackish ground 

waters are not limited to the Florida Peninsula but extend as 

far as 120 km from shore or to the edge of the shelf 

(Manheim and Hom, 1968; Manheim and Paull, 1981) 

(figs. 35.1 and 35.2). The U.S. Geological Survey (USGS) 

Atlantic Margin Coring Project (AMCOR) drill holes in 

1976 revealed that a freshwater to brackish-water tongue 

extended underneath the entire Atlantic shelf (Hathaway 

and others, 1979; Kohout and others, 1988). Unpublished 

studies by S.R. Riggs and F.T. Manheim (data on file at 

USGS offices in Woods Hole, Mass.) show that nearpotable water can be found even near the base of 6-m-long 

vibracores in Onslow Bay. This distribution of freshwater is 

linked with freshwater recharge during the exposure of the 

continental shelf during the Pleistocene glacial maximum. 

Freshwater lenses shield coastal ground-water resources 

from saline encroachment and are thus of great importance 

to coastal cities, such as Savannah, Ga., that rely upon 

ground water for their water supply. 

The nature and distribution of the offshore freshwater 

lenses in most areas are still poorly known and defined. 

Figure 35.1. Location of hydrochemical transect B-8', 

from Georgia to the Blake Plateau. COST, Continental 

Offshore Stratigraphic Test; JOIDES, joint Oceanographic 

Institute's Deep Earth Sampling; AMCOR, Atlantic Margin 

Coring Project. From Manheim and Paull (1981). Base map 

modified from Uchupi (1968). 

Potential Saltwater Intrusion into Freshwater Aquifers off the Southeastern United States 161 
en 

0::: 

w 

I--

w 

~ 

g 

~ 

I 

I--

a.. 

w 

0 

2 

3 

4 

PALEOZOIC METAMORPHICS 

0 50 

KILOMETERS 

11' 

\~ .... 

. . 

Figure 35.2. Hydrochemical transect 8-8' from land (Georgia) to Blake Plateau. Location of transect is indicated on figure 

35.1. Salinity contours are in grams per kilogram; dashed where inferred. Vertical lines refer to drill holes identified and 

discussed in Manheim and Paull (1981). 

They will require detailed examination and modeling in 

conjunction with offshore exploration and exploitation of 

potential mineral resources. Studies should be timed so that 

hydrologic models will be in place by the time leasing 

occurs. 

REFERENCES CITED 

Hathaway, J.C., Poag, C.W., Valentine, P.C., Miller, R.E., 

Schultz, D.M., Manheim, F.T., Kohout, F.A., Bothner, 

M.H., and Sangrey, D.A., 1979, U.S. Geological Survey 

core drilling on the Atlantic shelf: Science, v. 206, no. 

4418, p. 515-527. 

Kohout, F.A., Meisler, H., Meyer, F.W., Johnston, R.H., Leve, 

G. W., and Wait, R.L., 1988, Hydrogeology of the Atlantic 

continental margin, chap. 23, in Sheridan, R.D., and 

Grow, J.A., eds., The Atlantic continental margins, v. I-2, 

of The geology of North America (The Decade of North 

American Geology): Boulder, Colo., Geological Society of 

America, p. 463-480. 

Manheim, F.T., and Hom, M.K., 1968, Composition of deeper 

subsurface waters along the Atlantic continental margin: 

Southeastern Geology, v. 9, no. 4, p. 215-236. 

Manheim, F.T., and Paull, C.K., 1981, Patterns of groundwater 

salinity changes in a deep continental-oceanic transect off 

the southeastern Atlantic coast of the U.S.A., in Back, 

William, ed., Symposium on geochemistry of groundwater: 

Journal of Hydrology, v. 54, no. 1-3, p. 95-105. 

Riggs, S.R., 1984, Paleoceanographic model of Neogene phosphorite deposition---U.S. Atlantic continental margin: Science, v. 223, no. 4632, p. 123-131. 

Uchupi, Elazar, 1968, Atlantic continental shelf and slope of the 

United States-Physiography: U.S. Geological Survey Professional Paper 529-C, 30 p. 

162 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
36. Some Basic Facts About Radioactive Radon 

By joseph S. Duval and Allan B. Tanner 

Radioactive radon e22Rn) is produced naturally in 

most rocks and soils as part of the radioactive decay series 

of 238U (fig. 36.1). 222Rn has a half-life of 3. 823 days and 

can move significant distances from the site where it was 

produced. It can move about 1 m by diffusion in fractured 

rocks and permeable soils, and convection resulting from 

water or gas flow may increase the distance to 5 m or more. 

Radon can enter a house in a variety of ways (fig. 36.2). 

Once radon enters a house, it ultimately decays to 

produce three alpha-particle-emitting isotopes of polonium 

(see fig. 36.1). These alpha particles have been identified as 

an important cause of lung cancer when exposure levels 

were significant (National Council on Radiation Protection 

and Measurements (NCRPM), 1984). The unit of measure 

used to define exposure to radon daughter isotopes is the 

Working Level Month (WLM), which is defined as exposure to an average of 1 Working Level (WL) for a working 

month of 170 hours. WL is defined as a concentration of 

radon daughter isotopes that have a potential alpha energy 

release of 130,000 MeV (million electron volts) per liter of 

air. The exposure level can be estimated by a direct 

measurement of radon, and a radon concentration level of 

200 picocuries per liter (pCi/L) is approximately equivalent 

to 1 WL. The health risk of exposure to radon can be 

expressed as the number of excess lung cancer deaths in 

persons exposed to a particular level. NCRPM (1984) 

estimates that 0. 91 percent of people exposed to 1 WLM per 

year during their lifetime will die of lung cancer but that the 

effects of an exposure level of 0.2 WLM per year are 

minimal. This latter level implies that radon daughter 

concentrations equivalent to 0.004 WL can be considered 

safe for continuous, 24-hours-per-day exposure. The level 

currently being used as a guideline by the Environmental 

Protection Agency at remedial action sites is 0.02 WL 

(approximately 4 pCi/L of radon). 

The problem of defining and estimating the indoor 

radon hazard potential (H) can be expressed as the product 

of two functions: 

H=GXC 

EXPLANATION 

@ Lung cancer attributed to these a particles 

o Long -lived; geochemicolly independent 

• Measured in NURE airborne surveys 

Figure 36.1. 238U decay series. NURE, National Uranium Resource Evaluation. 

Some Basic Facts About Radioactive Radon 163 
Crawl Space 

Figure 36.2. Common paths of entry of radon into homes 

(from Sextro, 1985). 

where G is a geologic function that defines those parameters 

that control the availability of radon in the soil gas (see 

Otton, this volume) and C is a building-construction function that defines the parameters that control the entry of 

radon into a house. The form of these functions is presently 

unknown, and extensive research is being done to define 

them. The geologic function must include such parameters 

as the total radon in the soil gas, the total radon production 

rate, the emanating power of the geologic materials (the 

fraction of the total radon produced in the host materials that 

escapes into the soil gas), permeability, soil moisture, and 

convection resulting from gas or water flow. The total radon 

in the soil gas can be measured by suitable soil gas 

measurement techniques. The total radon production rate 

can be directly measured by using gamma-ray spectrometric 

techniques. The emanation power can also be directly 

measured in the laboratory, and field techniques can be 

developed. Permeability, soil moisture, and diffusion coefficients can be measured as well, but convection effects will 

be difficult to assess. The relative importance of the 

geologic parameters are not known and will require separate 

assessments. Existing data on indoor radon levels suggest 

that (1) high radium (parent of radon, fig. 36.1) concentrations result in high radon hazard potential, (2) normal 

radium concentrations and emanating power coupled with 

high porosity and permeability produce a high radon hazard 

potential, and (3) low porosity or water saturation results in 

low radon hazard potential. The construction function must 

include the effective permeability of the house (see fig. 

36.2) and the pressure differences across building-soil 

interfaces. Ventilation and barrier techniques have been 

shown to be effective in reducing the indoor radon concentration levels. 

REFERENCES CITED 

National Council on Radiation Protection and Measurements, 

1984, Exposures from the uranium series with emphasis on 

radon and its daughters: National Council on Radiation 

Protection and Measurements Report No. 77, 131 p. 

Sextro, R.G., 1985, Understanding the origin of radon indoorsBuilding a predictive capability: University of California, 

Lawrence Berkeley Laboratory Report LBL-20210, 

21 p. 

164 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
37. Geology of the Reading Prong, New York, and 

Its Application to Predicting Areas That Have 

High Radon Potential 

By Linda C. Gundersen 

Geologic and metallogenic models for uranium 

occurrences in the Reading Prong (Grauch, 1978; Gunderson, 1984, 1986) can be used to predict source areas for 

radon gas. Recent testing in Pennsylvania, New Jersey, and 

New York indicates that geologic factors strongly control 

the distribution of radon in homes and water supplies. 

Specifically, fault zones, highly uraniferous rocks, and 

uranium occurrences commonly associated with magnetite 

appear to be the major geologic influence. 

Some recently discovered elevated levels of radon in 

water supplies and in homes built on the Reading Prong 

illustrate the influence of geology on radon migration and 

accumulation. In Pennsylvania, one of the highest levels of 

radon gas ever recorded in a residential building was 

measured near Boyertown. The home was built directly on 

weathered Proterozoic bedrock over a uranium-rich shear 

zone. Radioactive decay of uranium was the most likely 

source for the radon, and the high transmissivity of the fault 

and high permeability of the weathered bedrock favored 

radon mobility. Elevated levels of radon in water have 

recently been discovered in Warwick, N.Y. Well water in 

this area comes from fractures in the Proterozoic rocks. 

Warwick has the largest radiometric anomaly on the 

National Uranium Resource Evaluation (NURE) aerial 

gamma-ray map of the Reading Prong (LKB Resources, 

Inc., 1980) and is known for its highly uraniferous magnetite deposits. In Fort Montgomery, N.Y., the soils are high 

in uranium and radon. Fort Montgomery is located on both 

a magnetic and a radiometric high and is the former site of 

one of the largest iron mines in New York. Uranium-rich 

material from the old magnetite mine probably caused the 

high uranium and radon in the soil. 

The Reading Prong physiographic province is composed of three subprovinces known as the Hudson Highlands in New York, the New Jersey Highlands in New 

Jersey, and the Reading Hills in Pennsylvania. The Proterozoic rocks underlying the Reading Prong are a sequence 

of volcanics and sediments that were metamorphosed during the Grenville orogeny (approximately 1 billion years 

ago) and syntectonic ally intruded by granites of different 

compositions. Parts of the Reading Prong were refolded 

during the Paleozoic. Systematic faulting and jointing 

occurred regionally during the Proterozoic, Paleozoic, and 

Mesozoic Eras. Recent geological investigations (Helenek, 

1971; Drake, 1984; Gundersen, 1985) have divided the 

Proterozoic rocks into distinct groups that are recognizable 

throughout the Reading Prong. They consist from bottom to 

top of the following stratigraphic units: (1) a calc-silicate 

gneiss, consisting of a basal hornblende amphibolite and 

pyroxene gneiss and minor quartz-feldspar gneiss, marble, 

and allanite- and scapolite-bearing gneisses; (2) a quartzoligoclase leucogneiss and minor hornblende and pyroxene 

amphibolite; (3) a hornblende gneiss; and (4) a predominantly metasedimentary sequence consisting of graphitic 

quartz-feldspar gneiss, graphitic biotite gneiss, biotitegarnet gneiss, and minor hornblende-feldspar gneiss, marble, and pyroxene gneiss. Pegmatites are ubiquitous in all 

the rocks and are the product of local anatexis. Leucogranite 

and hornblende granite locally intrude this sequence, and in 

the Hudson Highlands and the Reading Hills they constitute 

a significant part of the bedrock. A major Proterozoic 

marble belt, known as the Franklin Marble, extends along 

the western flank of the New Jersey Highlands and into 

easternmost Pennsylvania. 

Magnetite deposits, from which iron was produced in 

the 18th and 19th centuries, form concordant layers within 

the calc-silicate gneiss and hornblende gneiss in New York 

and New Jersey. In Pennsylvania and parts of New Jersey, 

magnetite deposits also occur in amphibolitic layers in the 

quartz-oligoclase leucogneiss and in the graphitic biotite 

gneiss. Iron- and copper-sulfide, uranium, thorium, phosphate, and rare-earth elements are associated locally with 

the magnetite deposits. Mining and exploration for uranium 

took place in the 1950's through the 1970's. 

Uranium, most commonly in the form of the mineral 

uraninite, occurs in three general host -rock associations: (1) 

magnetite-rich zones and deposits within the gneiss and 

associated faults and fractures; (2) granitic intrusives and 

Geology of the Reading Prong, New York, and Its Application to Predicting Areas That Have High Radon Potential 165 
URANIUM IN THE READING PRONG 

30 

KM 

Figure 37.1. Location of known uranium deposits in the 

Reading Prong. Closed circles represent magnetiteassociated uranium, open squares represent uranium 

hosted in granitic gneiss or pegmatite, and closed triangles represent uranium hosted in marble. 

pegmatites; and (3) marble (Grauch and Zarinski, 1976; 

Bell, 1983; Gundersen, 1984, 1986). In southern New York 

and northern New Jersey, the magnetite-associated uranium 

is the predominant type of show (fig. 3 7. 1). Rocks that are 

high in iron also tend to be high in uranium (fig. 37.2). In 

Pennsylvania, uranium occurs in magnetite-bearing zones, 

magnetite mines, serpentine deposits within the Franklin 

Marble, granite gneiss, and graphitic gneiss. 

The rock sequence (units 1-4 above) and mineral 

deposits just described may have originally been deposited 

in a Proterozoic marginal-marine basin as (1) mafic to 

intermediate volcanics, carbonate sediments, and exhalative 

iron-, sulfide-, and uranium-rich horizons; (2) silicic volcanics; (3) mafic volcanics and exhalative iron-, sulfide-, 

and uranium-rich horizons; and (4) silicic volcaniclastics, 

carbonaceous pelitic sediments, carbonate sediments, and 

minor exhalative iron-, sulfide-, and uranium-rich horizons. 

Similar sequences and mineral deposits are found in the 

Precambrian rocks of Canada, the northern midcontinent 

and East Coast of the United States, and in Australia, 

Scandinavia, China, and India. Many anorthosite-related 

extensional basin sequences, such as those that flank the 

Adirondacks, also host magnetite-associated uranium 

occurrences. In general, it appears that these types of 

deposits occur most frequently in marginal and cratonic 

extensional basins, usually of Precambrian age (Hauck and 

Kendall, 1984). 

The geologic and metallogenic model presented here 

can be used in the preliminary assessment of the Reading 

Prong to predict areas that have high radon potential. 

Quartz-oligoclase leucogneiss usually contains small 

amounts of uranium, whereas quartz-feldspar gneiss and 

granite have larger amounts of uranium. Magnetite ore, 

pyroxene gneiss, hornblende gneiss, pyroxene amphibolite, 

and graphitic biotite gneiss, especially those containing 

large amounts of iron, tend to have the highest uranium 

content. Uranium is also found in higher concentrations 

along the contacts between gneiss and granite intrusives and 

pegmatites. Major faults and fault junctions in the uraniferous gneisses and marbles are commonly mineralized with 

uranium and provide a conduit for the radon gas. Unconsolidated surficial materials, such as soil, alluvium, and 

glacial till, play a major role in radon transport from 

bedrock and fault sources into the foundations of buildings. 

Highly permeable surficial deposits increase the potential 

for high levels of radon accumulation. In New Jersey, much 

of the glacial till is derived from the underlying bedrock and 

may also serve as a source of radon. Current studies in the 

Reading Prong include the development of preliminary 

maps of radon potential based on bedrock geology, surficial 

geology, location of major fault zones, chemical and 

geophysical data, and geologic and metallogenic models for 

uranium. Future studies proposed for the Reading Prong 

include field measurements of radon migration through 

different types of soil and glacial deposits, the effects of 

permeability and moisture content on radon migration, the 

behavior of radon around faults, and the relation of the 

physical properties of bedrock and surficial materials to the 

amount of radon in the soil and homes. 

166 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
z 10,000-

0 

.....J 

.....J 8000- ~ 

a=::: 

L.U 

c.. 

(J) 6000-

ra=::: 

<( 

c.. 

z 4000-

~ 

:::J 2000-

z 

<( 

a=::: 

:::J o60 

rz 

L.U 

u 

a=::: 40 L.U 

c.. 

z 

z 

0 

a=::: 20 

0 

I I 

I I 

LG 

MG 

•• 

LG 

MG 

• 

• 

• 

I 

•• li. I I I I I 

HB OR HS 

A PE 

I 

I • 

• 

• • 1: 

I' I I 

I 

HB OR HS 

A PE 

Figure 37.2. Uranium in parts per million (ppm) 

and iron in percent versus rock type for metamorphic rocks from the Reading Prong, Greenwood Lake quadrangle, New York and New 

jersey. Rock types from left to right are quartzoligoclase leucogneiss (LG), melanocratic pyroxene gneiss (MG), hornblende gneiss (HB), 

amphibolite (A), magnetite ore (OR), pegmatite 

• 

• • 

• • 

I I • I I I I 

T T I I I I 

LG PS MB BC BGPG 

• • 

I· • • 

I 

• I I I 

I • I • 

LG PS MB BC BG PG 

(PE), hornblende gneiss having high iron and 

copper-sulfide content (HS), pyroxene leucogneiss (LG), pyroxene gneiss and pyroxene 

amphibolite having high iron and copper sulfide 

content (PS), marble (MB), brecciated pyroxene 

gneiss (BC), biotite gneiss (BG), and pyroxene 

gneiss having abundant magnetite (PG). 

Geology of the Reading Prong, New York, and Its Application to Predicting Areas That Have High Radon Potential 167 
REFERENCES CITED 

Bell, C., 1983, Radioactive mineral occurrences in New Jersey: 

New Jersey Geological Survey Open-File Report 83-5, 

21 p. 

Drake, A.A., 1984, The Reading Prong of New Jersey and eastern 

Pennsylvania-An appraisal of rock relations and chemistry of a major Proterozoic terrane in the Appalachians, in 

Bartholomew. M.J., ed .. The Grenville event in the Appalachians and related topics: Geological Society of America 

Special Paper 194. p. 94-109. 

Grauch, R.I., 1978. Geology of the uranium prospect at Camp 

Smith. New York, with a new model for the formation of 

uranium deposits in metamorphosed submarine volcanogenic rocks: U.S. Geological Survey Open-File Report 

78-949. 30 p. 

Grauch, R.I., and Zarinski. K., 1976, Generalized description of 

uranium-bearing veins, pegmatites. and disseminations in 

non-sedimentary rocks, Eastern United States: U.S. Geological Survey Open-File Report 76-582, 114 p. 

Gundersen, L.C., 1984, Geochemistry and geology of Precambrian rocks from the Greenwood Lake area, New York and 

New Jersey-Implications for the genesis of uraniummagnetite deposits [abs.]: Geological Society of America 

Abstracts with Programs. v. 16, no. 1, p. 16. 

---1985, Stratigraphy of the northern Reading Prong and its 

tectonic implications [abs.]: Geological Society of America 

Abstracts with Programs, v. 17. no. 1, p. 22. 

---1986, Geology and geochemistry of the Precambrian rocks 

of the Reading Prong, New York and New Jersey-Implications for the genesis of iron-uranium-rare earth deposits 

[abs.], in U.S. Geological Survey research on energy 

resources-1986 program and abstracts. 2d annual V.E. 

McKelvey Forum on Mineral and Energy Resources: U.S. 

Geological Survey Circular 974. p. 19. 

Hauck, S.A., and KendalL E.W., 1984. Comparison of middle 

Proterozoic iron oxide rich ore deposits, mid-continent 

U.S.A., South Australia, Sweden, and the Peoples Republic of China [abs.], in Proceedings, Annual Institute on 

Lake Superior Geology, April 24-28, 1984, Wausau, 

Wise.: p. 17-18. 

Helenek, H.L., 1971, An investigation of the origin, structure, 

and metamorphic evolution of major rock units in the 

Hudson Highlands: Providence, R.I., Brown University, 

unpub. Ph.D. dissertation. 

LKB Resources, Inc., 1980. Aerial gamma-ray and magnetic 

survey, Reading Prong area: U.S. Department of Energy, 

National Uranium Resource Evaluation Program, Contract 

78-234-6. GJBX 90 (80), v. 6. 1,715 p. 

168 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
38. The Role of National Uranium Resource 

Evaluation Aerial Gamma-Ray Data in 

Assessment of Radon Hazard Potential 

By joseph S. Duval 

National Uranium Resources Evaluation (NURE) 

aerial gamma-ray surveys measure the intensity of natural 

gamma rays emitted by members of the radioactive decay 

series of uranium, potassium, and thorium. The data from 

these surveys may be useful in trying to assess the hazard of 

radon in homes. In the uranium decay series, one of the 

daughter products is the radioactive gas radon (

222Rn). 226Ra, the last long-lived member of the series, has a 

half-life of 1,602 years (fig. 38.1). Radon has a half-life of 

3.823 days, which is short in geologic terms but is long 

enough to allow the gas to move significant distances from 

the point of origin if the host rock and (or) soil has high gas 

permeability. In soils, gas diffusion calculations (Tanner, 

1964; Fleischer and Likes, 1979) suggest that, prior to 

decaying, the radon can move distances of about 1 m or 

less; however, convection resulting from gas or water flow 

may increase the distances to 5 m or more in porous or 

fractured earth materials. The daughter products following 

radon (fig. 38.1) have half-lives ranging from 3.05 to 26.8 

minutes. One of these, 214Bi, produces the gamma rays that 

Figure 38.1. Portion of 238U decay series. 

are measured by the aerial gamma-ray system. Because 

their short half-lives prevent the daughter products, including radon, from traveling far from their parent in rocks or 

soils, the aerial gamma-ray surveys provide a direct measurement of the amount of radon produced in the nearsurface materials. These data do not, however, provide any 

direct information about how much of the radon produced is 

not retained in the host materials but is in the soil gas and 

free to move. 

Aerial gamma-ray measurements represent averages 

of the near-surface concentrations of radon. The materials 

that contribute more than 80 percent to the aerial measurement include the rock and soil to a depth of about 30 em 

over a circular area that has a radius approximately equal to 

twice the altitude of the aircraft (Duval and others, 1971). 

The surface area included in the average varies as a function 

of the height of the gamma-ray detector above the ground 

surface (fig. 38.2). Many aerial gamma-ray surveys are 

flown approximately 400 feet above the ground. This was 

true for the surveys flown as part of the U.S. Department of 

Energy NURE Program. The percentage of the surface area 

actually measured by a survey is a function of the 

500.-------------------------------------~ 

0 

0 

o_ 

,.... 400 

X 

N 

"0 

~ 

0 300 u.J 

c.:: 

::l 

Vl 

< u.J 

~ 200 

~ c.:: 

< 

u.J 100 u 

< u... 

c.:: 

::l 

Vl 

0 0 200 400 600 800 1 000 

DETECTOR HEIGHT ABOVE GROUND (ft) 

Figure 38.2. Surface area measured as a function of the 

height of the detector. 

The Role of National Uranium Resource Evaluation Aerial Gamma-Ray Data in Assessment of Radon Hazard Potential 169 
1oon-------------------------------------~ 

90 

80 

70 

60 

50 

40 

30 

20 

10 

0~~~--~~==~~~~~~~ 0 3 4 5 6 7 8 10 FLIGHT-LINE SPACING (mi) 

Figure 38.3. Percentage of surface area covered versus the 

flight-line spacing. 

flight-line spacing used (fig. 38.3). Because most of the 

NURE surveys had flight-line spacing of 3 or 6 miles, they 

provide data for less than 10 percent of the surface area. 

Although this amount of coverage is not sufficient for 

extensive site-specific assessments, the data can be used to 

generate regional-scale maps and to provide site-specific 

information along the flight lines. 

The NURE data can be presented in the form of 

contour maps or flight-line profiles of the near-surface 

equivalent uranium (eU), potassium (K), and equivalent 

thorium (eTh) concentrations. The term "equivalent," 

denoted by the lowercase "e," emphasizes that both the 

uranium and thorium decay series have a potential for 

radioactive disequilibrium caused by differences in chemical behavior among the various daughter nuclides. These 

maps and profiles can be used to identify areas where the 

uranium concentrations are relatively high; however, they 

provide no indication of the radon emanation power of the 

materials, which is a measure of the ratio of the radon in the 

soil gas to the total amount of radon produced. Duval 

( 1983) developed a technique that combines the uranium 

concentration data with the eU:K and eU:eTh to produce 

composite-color uranium maps. The assumption used to 

interpret these maps is that high values of all three parameters (eU, eU:K, and eU:eTh) indicate that uranium concentration has occurred. If the uranium has been concentrated by metamorphic, igneous, hydrothermal, or lowtemperature aqueous processes, the radon hazard potential 

may be enhanced. The concentration maps, profiles, and 

composite-color maps can be used to provide an initial 

classification of the surface rock and soil regarding radon 

hazard potential. This classification will have to be modified and improved by using geologic data and measurements of the radon concentrations in soil gas. 

REFERENCES CITED 

Duval, J.S., 1983, Composite color images of aerial gamma-ray 

spectrometric data: Geophysics, v. 48, no. 6, p. 722-735. 

Duval, J.S., Cook, B.G., Adams, J.A.S., 1971, Circle of 

investigation of an airborne gamma-ray spectrometer: Journal of Geophysical Research, v. 76, p. 8466-8470. 

Fleischer, R.L. and Likes, R.S., 1979, Integrated radon monitoring by the diffusional barrier technique: Geophysics, v. 44, 

no. 12, p. 1963-1973. 

Tanner, A.B., 1964, Radon migration in the ground-A review, 

in Adams, J.A.S., and Lowder, W.M., eds., The natural 

radiation environment: Chicago, Ill., University of Chicago 

Press, p. 161-190. 

170 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
39. Potential for Indoor Radon HazardsA First Geologic Estimate 

By James K. Otton 

INTRODUCTION 

Two principal factors that determine the level of 

radon in a dwelling are ( 1) the availability of radon in the 

ground and (2) the structural characteristics of the dwelling. 

Of these, only the availability factor is a function of the 

natural environment and is the only one considered here. 

Although high radon levels in specific buildings may be 

caused by the use of uranium-rich and radium-rich natural 

building materials or by the degassing of radon-rich waters 

in showers and other devices in the home, the principal 

natural source of indoor radon is soil gas that moves into the 

dwelling through the foundation by diffusion or by flow 

caused by air-pressure differences. Subjacent bedrock is 

usually a major contributor of radon also, especially where 

soils are thin or where the bedrock is uranium or radium 

enriched and permeable. The availability of radon in soil 

gas is dependent on the radium concentration in the soil and 

bedrock, the emanating power of the soil (that fraction of 

the radium in mineral grains that produces radon in soil 

pores), the soil porosity and permeability, and the moisture 

content of the soils. 

The radium content of soils and bedrock is a result of 

a series of complex water and rock interactions in the 

uranium geochemical cycle that involves leaching of uranium and its daughter products from their sources, transport 

of these elements in surface and ground waters, and fixation 

of the elements in a host. Radon is the product of a decay 

chain of geochemically distinctive radioelements. Most of 

the radioelements in that chain are cations soluble in and 

largely transported by water, but radon is an inert gas that 

can be transported by either water or air. 

Because a radon problem starts with radon's availability in the ground, an understanding of the geology and 

geochemistry of uranium and radium and an understanding 

of the geology and physical properties of soils should make 

it possible to predict where radon hazards may occur. 

However, the interplay between radium concentrations in 

soils and subjacent bedrock and the porosity and permeability of the soils, although critical, has been little studied. 

Case studies do suggest, however, that high concentrations 

of uranium and radium in soils and subjacent bedrock can 

cause severe radon problems (greater than 1 Working Level 

(1 WL) or 200 picocuries per liter (pCi/L)) in indoor air no 

matter what the soil characteristics. High concentrations of 

uranium in bedrock are the causes of the highly publicized 

radon hazards in residences in the Boyertown, Pa., area of 

the Reading Prong (Robert Smith, written commun., 1986) 

and in residences built over certain granites and most alum 

shales in Sweden (Akerblom and others, 1984). However, 

highly porous and permeable soils can cause elevated radon 

concentrations (0 .1 to 1 WL or 20 to 200 pCi/L) even if the 

uranium and radium concentrations in a soil are only 

average, simply because large volumes of soil gas may 

move into buildings through permeable soils. For example, 

houses constructed on glacial outwash gravels and eskers 

have been documented as having high levels of indoor 

radon in some areas of the United States and in many areas 

of Sweden. Conversely, heavy clay soils and sediments, 

especially where water saturated, can nearly block all 

soil-gas migration. 

GEOLOGIC SITUATIONS THAT MAY 

PRODUCE ELEVATED INDOOR RADON LEVELS 

The existing information on uranium and radium 

geology and geochemistry, including the National Uranium 

Resource Evaluation (NURE) aeroradiometric data (J.S. 

Duval, written commun., 1986), and studies of radon soil 

gas and indoor radon strongly suggest that terrane overlying 

uranium occurrences has the highest probability of producing severe radon levels in indoor air (greater than 1 WL or 

200 pCi/L). These data also show that certain rock types are 

known to contain uranium concentrations above the average 

for most rocks. These rock types are likely to contain 

elevated radon concentrations in soils and weathered bedrock across their outcrop area but are not likely to produce 

severe levels. In some cases, unusually high permeability of 

the underlying rocks increases the radon hazard potential. 

On the basis of present information, the geologic terranes 

listed below are believed to have an increased likelihood for 

producing significantly elevated radon concentrations in 

homes. 

Potential for Indoor Radon Hazards-A First Geologic Estimate 171 
Granitic and Metamorphic Terranes 

Example A. The Reading Prong of Pennsylvania, 

New York, New Jersey, and Connecticut.-Anomalously 

uraniferous Proterozoic? metamorphic rocks and local uranium occurrences of the Reading Prong have produced high 

average levels and locally severe radon levels in some 

homes in Pennsylvania. The national index home for radon 

(13 WL) is located in this province near Boyertown, Pa. 

Geologically similar terranes exist elsewhere in the Eastern 

United States (Grauch and Zarinski, 1976), but these other 

areas are largely unevaluated. 

Example B. Glaciated Paleozoic granitic and 

high-grade metamorphic terranes in Maine and New 

Hampshire. -Radon problems in ground waters associated 

with anomalously uraniferous granites and high-grade metamorphic terranes were initially identified in Maine (Brutsaert and others, 1981) and New Hampshire (F. Hall, 

University of New Hampshire, oral commun., 1986). 

Subsequently, elevated indoor-air radon concentrations 

were identified in Maine (M. Lanctot, Maine Geological 

Survey, oral commun., 1986). Similar areas exist throughout the Eastern United States, but many of them are not 

glaciated and instead are deeply weathered. The effects of 

deep weathering on radium geochemistry and radon movement in soils need to be evaluated. 

Phosphate Lands 

Reclaimed phosphate mining areas in Florida were 

recognized in early studies as radon problem areas. Subsequent work has shown that unmined phosphate lands in 

these same areas have similar if not higher radon levels in 

homes (Florida Department of Health and Rehabilitative 

Services, 1978). Phosphate lands exist elsewhere in the 

United States but have been less thoroughly evaluated for 

radon problems. 

Pleistocene and Holocene Glacial Outwash 

Gravels 

These sediments are unusually permeable and form 

soils that also are unusually permeable. Elevated levels of 

radon are common in the east Spokane, Wash., and the 

northern Idaho areas that are underlain by such gravels, 

especially where the gravels are derived from granitic 

rocks. Locally, radon values in houses may approach severe 

levels (Lawrence Berkeley Laboratory, written commun., 

1986). 

Glacial Till and Moraine, Loess, and Lacustrine 

Clay 

Although these sediments are generally poorly sorted 

and low in permeability, they are locally highly permeable 

or are locally very fine grained and have high radonemanating power. Thus, even though they are not always 

high in uranium or radium concentrations, soils over these 

sediments may have high radon availability. Radon levels 

can be elevated where these sediments are derived from 

uraniferous rocks such as granites or marine shales. A few 

indoor and soil-gas radon studies over these sediments in 

the North-Central States suggest locally high values for 

radon (see, for example, the newspaper Fargo Forum, Oct. 

20, 1985). 

Carbonate Terranes, Especially Karst Cave Areas 

Caverns and caves in the National Park Service 

system have been evaluated for radon hazards, and a 

significant number of them have hazardous levels of radon 

(Yarborough, 1980). Some caves contain several working 

levels of radon. Although limestones and dolomites generally do not contain elevated levels of uranium or radium, 

they commonly contain phosphatic material, lenses of 

carbonaceous mudstone, or volcanic ash. Uranium contents 

are higher where these other materials are present. In 

addition, the clays and iron oxyhydroxides that form the 

principal weathering products of limestones and dolomites 

are very effective adsorbents of uranium and radium. The 

high permeability of weathered limestones and the fine 

grain size of these weathering products also make them very 

efficient radon emitters. The few studies of indoor air and 

soil gas that have been conducted in carbonate terranes 

suggest that a significant percentage of the values are 

elevated (Sachs and others, 1982), and possibly some are 

locally severely elevated. Carbonate rocks are found over 

wide areas of the Central and Eastern United States. 

Marine Black Shales, Especially Devonian Shales 

of the Central United States 

These rocks have long been known for their elevated 

uranium concentrations. One study of soil gas and indoor 

air in part of New York State suggests that elevated radon 

concentrations exist over these rocks (Lilley, 1985). Similar, although more uraniferous, rocks in Sweden have been 

identified as a major radon hazard (Akerblom and others, 

1984). Again, marine black shales are widely distributed 

and underlie parts of major population centers, especially in 

the Central United States. Other types of marine shales, for 

example, the Pierre Shale of the Western United States, 

contain slightly elevated uranium concentrations and may 

create some radon hazards. 

172 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Arkosic and Volcaniclastic Alluvial 

Conglomerates and Sandstones 

Such rocks exist in several areas of the country in 

terranes that range from Proterozoic? to Holocene age. 

Areas in which uranium concentrations are known to be 

elevated include parts of basins adjacent to the Front Range 

of Colorado, parts of the Mesozoic basins of the Eastern 

United States, the areas underlain by the Ogallala and White 

River Fo~ations of the High Plains of Texas, Nebraska, 

and elsewhere, and many intermontane basins in the Westem United States, notably in Wyoming and Montana. Many 

of these units host uranium occurrences and deposits. 

Locally. radon levels may be more severe in homes near 

uranium occurrences, and generally there may be elevated 

radon values. A few studies of uranium in waters and of 

radon in waters, soil gas, and indoor air in some of these 

areas suggest that concentrations of radon significantly 

above the national norm may be expected. 

CONCLUSIONS 

This list must be regarded as only a first compilation. 

It must be emphasized that not every building over one of 

these rock types has elevated radon levels. Many sources of 

variability affect radon levels in bedrock, soil gases, and 

inside structures. For example, granites vary in their uranium content. Considerable variability is attributable to 

housing factors. Much work is required on each of these 

types of terranes. as well as on other terranes, to establish 

whether radon hazards exist and, if they do, to determine 

their extent and their causes. Other rock types may also 

produce radon hazards, and each of these potential sources 

must be evaluated. 

REFERENCES CITED 

Akerblom, G., Andersson, P., and Clavensjo, B., 1984, Soil gas 

radon-A source for indoor radon daughters: Radiation 

Protection Dosimetry, v. 7, no. 1-4, p. 49-54. 

Brutsaert, W.F., Norton, S.A., Hess, C.T., and Williams, J.S., 

1981, Geologic and hydrologic factors controlling radon222 in ground water in Maine: Ground Water, v. 19, p. 

407-417. 

Florida Department of Health and Rehabilitative Services, 1978, 

Study of radon daughter concentrations in structures in Polk 

and Hillsborough Counties: Tallahassee, Fla., Florida 

Department of Health and Rehabilitative Services, 110 p. 

Grauch, R.I., and Zarinski, Katrin, 1976, Generalized descriptions of uranium-bearing veins, pegmatites, and disseminations in non-sedimentary rocks, Eastern United States: U.S. 

Geological Survey Open-File Report 76-582, 114 p. 

Lilley, W. D., 1985, A geological assessment of houses monitored 

for radon in central New York State: Geological Society of 

America Abstracts with Programs, v. 17, no. 1, p. 32. 

Sachs, H.M., Hernandez, T.L., and Ring, J.W., 1982, Regional 

geology and radon variability in buildings: Environment 

International, v. 8, p. 97-103. 

Yarborough, K.A., 1980, Radon- and thoron-produced radiation 

in National Park Service caves, in The natural radiation 

environment, III: U.S. Department of Energy CONF 

780422, p. 1371-1395. 

Potential for Indoor Radon Hazards-A First Geologic Estimate 173 

40. Hazards Associated with Fibrous Minerals 

By Malcolm Ross 

THE ASBESTOS PROBLEM 

The widespread use of amphibole and serpentine 

asbestos by our industrial society has contributed greatly to 

human safety and convenience. Yet, while society was 

accruing these very tangible benefits, many asbestos workers were dying of asbestosis, lung cancer, and mesothelioma. The hazards of certain forms of asbestos under 

certain conditions have been so great that several countries 

have taken extraordinary actions to greatly reduce or even 

ban their use. Recent experiments with animals, however, 

demonstrate that other fibrous materials can cause the 

formation of tumors when such particles are implanted 

within the pleural tissue. These experiments have convinced 

some health specialists that asbestos-related diseases can be 

caused by many types of elongate particles; the mineral 

type, according to these health specialists, is not the 

important factor in the etiology of disease, but rather the 

size and shape of the particles that enter the human body. 

In the United States, the most widely used definition 

of asbestos for regulatory purposes comes from the Federal 

Register (October 9, 1975, p. 47652-47660). In this notice, 

the naturally occurring amphibole minerals amosite, crocidolite, anthophyllite, tremolite, and actinolite and the serpentine mineral chrysotile are classified as asbestos if the 

individual crystallites or crystal fragments have the following dimensions: a length greater than 5 micrometers, a 

maximum diameter less than 5 micrometers, and a lengthto-diameter ratio of 3 or greater. The crushing and milling 

of any rock usually produces some mineral particles that are 

within the size range specified in Federal rules. Thus, these 

regulations present a formidable problem to those analyzing 

for asbestos minerals in the multitude of materials and 

products in which they may be found in some amount. 

THE NATURE OF ASBESTOS-RELATED DISEASE 

The three principal diseases related to asbestos are ( 1) 

lung cancer, (2) mesothelioma (cancer of the pleural and 

peritoneal membranes), and (3) asbestosis, a condition in 

which the lung tissue becomes fibrous and thus loses its 

ability to function. These diseases, however, are not equally 

prevalent in the various groups of asbestos workers that 

have been studied; the amount and type of disease depends 

on the duration of exposure, on the intensity of exposure, 

and, particularly, on the type or types of asbestos to which 

the individual has been exposed, generally chrysotile, 

crocidolite, and (or) amosite (Simpson, 1979; Dupre, 

1984). 

Chrysotile asbestos (white asbestos) is the form that is 

usually used in the United States as wall coatings, in brake 

linings, as pipe insulation, and in other uses. About 95 

percent of the asbestos in place in the United States is the 

chrysotile variety, and a large percentage of this was mined 

and milled in Quebec Province, Canada. Epidemiological 

studies of the chrysotile asbestos miners and millers of 

Quebec show that, for men exposed for more than 20 years 

to chrysotile dust averaging 20 fibers per cubic centimeter 

of air, the total mortality was less than expected (620 

observed deaths, 659 expected deaths); the risk of lung 

cancer was slightly increased ( 48 deaths observed, 42 

expected). Exposures to air containing 20 fibers per cubic 

centimeter are an order of magnitude greater than those 

experienced now, which are generally less than 2 fibers per 

cubic centimeter; thus, chrysotile miners working a lifetime 

under these present dust levels should not be expected to 

suffer any measurable excess cancer. Mesothelioma incidence among those working only with chrysotile asbestos is 

very low; thus far, about 16 deaths due to this disease have 

been reported among chrysotile asbestos miners and millers 

and one death among chrysotile trades workers (Dupre, 

1984, p. 173-178; Ross, 1984, p. 91-93). Four epidemiological studies of the female residents of the Quebec 

chrysotile mining localities who did not work in the 

asbestos industry show no statistically significant evidence 

that their lifelong exposure to asbestos dust from the nearby 

mines and mills has caused excess disease (Siemiatycki, 

1982; Ross, 1984, p. 81-86). 

Crocidolite asbestos (blue asbestos) was first 

imported into the United States in 1912. Epidemiological 

studies of groups that worked only with crocidolite asbestos 

show that rather short periods of exposure, or even relatively light exposure, causes excessive mortality due to lung 

cancer, mesothelioma, and asbestosis. This hazard is evident not only in those exposed to crocidolite during gasHazards Associated with Fibrous Minerals 175 
mask fabrication and building construction but in those 

employed in the croci do lite mines. Mesothelioma is a 

significant cause of death in only two crocidolite mining 

regions-the Cape Province, South Africa, and Wittenoom, 

Western Australia. Studies accomplished in the Cape Province show that at least 278 people have died of mesothelioma as a result of exposure to crocidolite; of these people, 

161 worked in the mines and mills, and 117 lived in the 

vicinity of the mines but were not employed in the asbestos 

industry (Ross, 1984, p. 79-80). 

All amosite asbestos (brown asbestos) comes from 

the Transvaal Province of South Africa, where, between 

1917 and 1979, approximately 2.2 million tonnes were 

mined. Importation of amosite into the United States started 

in the 1930's. The incidence of asbestos-associated disease 

in two groups of amosite workers formerly employed at 

factories in London, England, and Patterson, N.J., was 

excessive, there being a 18.4 percent lung cancer mortality 

(117 cases), a 2.8 percent mesothelioma mortality (8 cases), 

and 4.2 percent asbestosis mortality (27 cases). Only 

prevalence studies have been made of amosite miners and 

millers; two individuals have died of mesothelioma. One 

resident of an amosite mining district has been reported as 

having died of this disease. 

The rock-forming amphibole minerals grunerite and 

cummingtonite, which are isostructural and chemically 

similar to amosite (a varietal name for grunerite asbestos), 

are considered incorrectly by some to be forms of asbestos. 

Health studies of men mining ores that contain these 

minerals as gangue do not show any indication of asbestosrelated mortality; for example, the Homestake gold miners 

and the Reserve iron-ore miners (Ross, 1981, 1984). 

DISCUSSION 

Nonoccupational exposure to chrysotile asbestos, 

despite its wide dissemination in urban environments 

throughout the world, has not been shown by epidemiological studies to be a significant health hazard. The same fiber 

dose-disease response relations observed for chrysotile 

asbestos do not hold for crocidolite asbestos. Health studies 

of trades workers exposed to only crocidolite show it to be 

much more hazardous than chrysotile. 

The fear caused by the much exaggerated predictions 

of the amount of asbestos-related mortality expected in the 

next 20 or 30 years has generated great political pressure to 

remove asbestos from our environment and to greatly 

reduce or even stop its use. An example of this is the 

concerted effort in several industrial nations, including the 

United States, to remove asbestos from schools, public 

buildings, homes, ships, appliances, and so forth. This 

removal is being done, even though most asbestos is of the 

chrysotile variety and even though asbestos dust levels in 

schools, public buildings, and city streets are much lower 

than those found in chrysotile asbestos mining communities, where no asbestos-related disease has been noted in the 

nonoccupationally exposed residents. The impetus for these 

costly removals and appliance recalls (hair dryers, for 

example) apparently comes from the "zero threshold" concept of cancer induction. 

Some health and regulatory specialists classify the 

common rock-forming amphiboles grunerite, cummingtonite, actinolite, tremolite, and anthophyllite as asbestos 

even though they do not possess the physical properties 

requisite to be valuable commercially. Such a classification 

has been made in the case of taconite mining by the U.S. 

courts. Thus far, however, asbestos-related disease has not 

been associated with any mining industry other than commercial asbestos mining. 

The possible health effects of exposure to rock dust 

containing one or more of the many amphibole minerals are 

an important issue. Amphiboles are contained within the 

gangue of many hard-rock mines-gold, vermiculite, talc, 

iron ore, crushed stone and aggregate, copper, and so forth. 

Certainly, control of most dust, regardless of the mineral 

content, is necessary because past heavy exposure to dusts 

containing crystalline silica, slate, coal, talc, and radioactive minerals has caused significant disease. Unusually tight 

control of amphibole mineral particles, such as was proposed by the National Institute for Occupational Safety and 

Health in 1976 for asbestos fibers (0.1 fiber per cubic 

centimeter), however, may stop major mining in the United 

States. 

REFERENCES CITED 

Dupre, J.S., 1984. Report of the Royal Commission on matters of 

health and safety arising from the use of asbestos in 

Ontario: Toronto, Ontario, Ministry of the Attorney General. v. L p. 1-313; v. 2, p. 314-684; v. 3, p. 685-920. 

Ross, Malcolm, 1981, The geologic occurrences and health 

hazards of amphibole and serpentine asbestos, in Amphiboles and other hydrous pyriboles-Mineralogy: Washington, D.C., Mineralogical Society of America, p. 279-323. 

---1984, A survey of asbestos-related disease in trades and 

mining occupations and in factory and mining communities 

as a means of predicting health risks of nonoccupational 

exposure to fibrous minerals: American Society of Testing 

and Materials Special Technical Publication 834, 

p. 51-104. 

Siemiatycki, Jack. 1982, Health effects on the general population 

(mortality in the general population in asbestos mining 

areas), in Proceedings of the World Symposium on Asbestos, Montreal, May 25-27, 1982: Montreal, Canadian 

Asbestos Information Centre, p. 337-348. 

Simpson. William. 1979, Asbestos; v. 1, Final report of the 

advisory committee; v. 2, Papers commissioned by the 

committee: London, Health and Safety Commission, v. 1, 

100 p.; v. 2, 103 p. 

176 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
41. Environmental Concerns Related to Selenium 

in the Western United States 

By ]ames M. McNeal, Gerald L. Feder, William G. Wilber, and Stephen]. Devere! 

The form of elements in the natural environment is 

vitally important in determining their potential for harmful 

effects to living organisms. Selenium is as an excellent 

example. Even though the mean concentration of selenium 

in weathered surficial materials is greater in the Eastern 

United States than in the Western United States (300 and 

230 parts per billion (ppb) selenium, respectively; Shacklette and Boerngen, 1984), selenium toxicity problems are 

most prevalent in the Western United States, whereas 

selenium deficiency problems are most prevalent in the 

Eastern United States. The reason for this reversal is the 

difference in the chemical form of selenium in the environment and the resultant difference in the ease of aqueous 

transport of selenium and its availability for plant uptake. 

This paper discusses the environmental geochemistry of 

selenium and its relation to environmental effects. This 

discussion will underscore the importance of the forms of 

trace elements in understanding, and perhaps predicting and 

ameliorating, the potentially harmful effects of some elements to the environment. 

Environmental problems involving naturally occurring selenium are widespread and have been known for a 

long time. Rosenfeld and Beath (1964) noted that Marco 

Polo may have encountered selenium-toxicity problems on 

his travels to China. They also gave an account of selenium 

problems in the Western United States and in several other 

semiarid regions of the world. Even though seleniumtoxicity problems are most prevalent in semiarid regions, 

they may also exist in humid temperate and tropical regions, 

for example, Ireland and Columbia (Rosenfeld and Beath, 

1964). 

Selenium is necessary as a trace nutrient to man, but 

it may also cause toxic effects when ingested in large 

amounts. In livestock, detrimental effects are known to be 

caused by selenium in both deficient and excessive 

amounts. Consequently, much has been written on selenium 

deficiency and toxicity, particularly in the field of animal 

nutrition. General texts on selenium include those by 

Trelease and Beath (1949), Rosenfeld and Beath (1964), 

and Zingaro and Cooper (1974). Excellent reviews of the 

natural occurrence of selenium and selenium geochemistry 

have been written by Lakin (1972, 1973) and Lakin and 

Davidson (1973). Mineral deposits containing selenium 

have been discussed by Sindeeva (1964). 

The forms of selenium, and other elements, are 

dependent largely on the pH, the oxidation state, and the 

chemical constituents of the environment. Geering and 

others ( 1968) showed that the weathering of selenium from 

rocks and its accumulation in soils or ground water depends 

on the oxidation state and pH of the environment. Some 

rocks are known to be sources of selenium. For example,. 

some black shales (Lakin, 1973; Leventhal and Hosterman, 

1982) and phosphatic deposits (Lakin, 1973) are known to 

contain high concentrations of selenium. 

Selenium predominantly occurs in four forms in the 

natural environment (Geering and others, 1968). The highly 

soluble selenate (SeO/-) is the form of selenium found in 

alkaline oxidizing environments. This form of selenium can 

be readily transported in solution and may be concentrated 

in closed basins and other areas, particularly in the arid 

West. As selenate, selenium is readily available for uptake 

by plants and may concentrate in large amounts in some 

plants (Rosenfeld and Beath, 1964). 

In more acidic environments, selenium tends to occur 

as selenite (SeO/-) ion, which is not as soluble as selenate. 

Selenite selenium generally occurs as the insoluble basic 

ferric selenite or may be immobilized by sorption on iron 

oxyhydroxides. These latter conditions exist largely in the 

Eastern United States, where the concentration of selenium 

available to plants may be low. Forage crops grown in these 

areas sometimes cause selenium deficiency problems in 

livestock and require the addition of selenium supplements 

to the soil (Oldfield, 1972). 

In more reducing environments, selenium may occur 

as the metal (Se0 ) or the selenide (Se2-) ion. As selenide, 

selenium may substitute for sulfur in pyrite or other sulfide 

minerals or may form selenide minerals, for example, 

tiemannite (HgSe). These forms of selenium are generally 

immobile in most natural environments, and the rates of 

transformation between the different forms are slow. Microorganisms are known to reduce selenite to metallic selenium 

(Ganther, 1974). 

Environmental Concerns Related to Selenium in the Western United States 177 
The organic chemistry of selenium is similar to that of 

sulfur. As sulfur is an important constituent of plant and 

animal tissue (Lakin, 1973), selenium may also be readily 

incorporated into plant and animal tissue (Ganther, 1974). 

Some plants, known to accumulate high concentrations of 

selenium, may be toxic to animals when eaten (Trelease and 

Beath, 1949; Rosenfeld and Beath, 1964; Ganther, 1974). 

A relation between the organic content of soils in Ireland 

and elevated concentrations of selenium was found by 

Fleming ( 1962). However, the form of the selenium in the 

organic material was not determined. Lakin (1972) noted 

that selenium associated with the organic material of soils 

occurs as seleniferous proteins, elemental selenium, and 

selenite. A report on the biochemistry of selenium by 

Ganther (1974) may be helpful in guiding research on the 

forms of selenium in the natural environment, which are not 

well known. 

The well-known selenium-toxicity problem at the 

Kesterson Wildlife Refuge in the west -central part of the 

San Joaquin Valley in California is due, at least in part, to 

the mobility of selenium in ground water from adjacent 

irrigated lands (Deverel and others, 1984). Selenium has 

been concentrated by evaporation in the areas that have 

been irrigated over the last 20 to 50 years. Farm drainage 

systems, which have been installed in some of the irrigated 

areas in the last 10 to 20 years, are now removing this 

shallow ground water containing high concentrations of 

selenium. Current irrigation water provides the hydraulic 

head necessary to cause the shallow ground water to flow. 

The accumulation of selenium in Kesterson probably is 

associated with the discharge of the drainage waters, 

transmitted by the San Luis Drain, which flow into Kesterson. Analysis of water samples collected at several sites 

(Deverel and others, 1984) showed selenate to represent 

over 80 percent of the total dissolved selenium in the 

sample. 

Current environmental concerns with selenium have 

shown that studies of total element concentrations alone are 

not satisfactory in evaluating the potential for environmental problems. Most of what is known about selenium in the 

environment, however, is based on the total concentration 

of selenium, not on the form of selenium. In addition, the 

reactions between the various forms of selenium and the 

constituents of rocks, soils, and sediments (for example, 

iron oxyhydroxides, manganese oxyhydroxides, organic 

material, clay minerals, and so on) are not well known. 

Studies similar to those for selenium should be undertaken 

for arsenic, molybdenum, uranium and vanadium, among 

others, because they behave in a geochemical manner 

similar to that of selenium and may also cause environmental problems. 

REFERENCES CITED 

Devere!, S.J., Gilliom, R.G., Fuji, Roger, Izbicki, J.A., and 

Fields, J. C., 1984, Areal distribution of selenium and other 

inorganic constituents in shallow ground water of the San 

Luis Drain Service Area, San Joaquin Valley, California-A preliminary study: U.S. Geological Survey Water 

Resources Investigations Report 84-4319, 67 p. 

Fleming, G .A., 1962, Selenium in Irish soils and plants: Soil 

Science, v. 94, p. 28-35. 

Ganther, G.W., 1974, Biogeochemistry of selenium, in Zingaro, 

R.A., and Cooper, W.C., eds., Selenium: New York, Van 

Nostrand Reinhold Company, p. 546-614. 

Geering, H.R., Cary, E.E., Jones, H.P., and Allaway, W.H., 

1968, Solubility and redox criteria for the possible forms of 

selenium in soils: Soil Science Society of America, Proceedings, v. 32, p. 35-40. 

Lakin, H. W., 1972, Selenium accumulation in soils and its 

absorption by plants and animals, in Cannon, H.L., and 

Hopps, H.C., eds., Geochemical environment in relation to 

health and disease: Geological Society of America Special 

Paper 140, p. 45-53. 

---1973, Selenium in our environment, in Kothny, E.L., ed., 

Trace elements in the environment: American Chemical 

Society, Advances in Chemistry Series No. 123, 

p. 96-111. 

Lakin, H.W., and Davidson, D.F., 1973, Selenium, in Brobst, 

D.A., and Pratt, W.P., eds., United States mineral 

resources: U.S. Geological Survey Professional Paper 820, 

p. 573-580. [Reprinted 1981.] 

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

mineralogical analysis of Devonian black-shale samples 

from Martin County, Kentucky; Caroll and Washington 

Counties, Ohio; Wise County, Virginia; and Overton 

County, Tennessee, U.S.A.: Chemical Geology, v. 37, no. 

3-4, p. 239-264. 

Oldfield, J .E., 1972, Selenium deficiency in soils and its effect on 

animal health, in Cannon, H.L., and Hopps, H.C., eds., 

Geochemical environment in relation to health and disease: 

Geological Society of America Special Paper 140, 

p. 57-63. 

Rosenfeld, Irene, and Beath, O.A., 1964, Selenium-Geobotany, 

biochemistry, toxicity, and nutrition: New York, Academic 

Press, Inc., 411 p. 

Shacklette, H.T., and Boemgen, J.G., 1984, Element concentrations in soils and other surficial materials of the conterminous United States: U.S. Geological Survey Professional 

Paper 1270, 105 p. 

Sindeeva, N.D., 1964, Mineralogy and types of deposits of 

selenium and tellurium: New York, Interscience Publishers, 363 p. 

Trelease, S.F., and Beath, O.A., 1949, Selenium-Its geological 

occurrence and its biological effects in relation to botany, 

chemistry, agriculture, nutrition, and medicine: New York, 

published by the authors, 292 p. 

Zingaro, R.A., and Cooper, W.C., eds., 1974, Selenium: New 

York, Van Nostrand Reinhold Company, 835 p. 

178 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
42. Copper-Molybdenum Imbalances and the 

Incidence of Nutritional Diseases in Livestock 

and Humans 

By James A. Erdman 

In December 1985, the journal Minerals and the 

Environment changed its name to Environmental Geochemistry and Health. In an editorial marking this change, 

Davies ( 1985, editorial page) said: 

The composition of food and water are influenced by 

that of soil which, in tum, depends on the geochemical nature 

of bedrock. Some rocks naturally contain high concentrations 

of certain trace elements whereas others are almost devoid of 

them. These natural geochemical variations are further complicated by localized accumulations of elements, such as 

cadmium or lead, which arise as a consequence of man's 

urban, industrial, and mining activities. Some trace elements 

are essential for mammalian metabolism and deficiencies of 

them may limit the activities of key enzyme systems or the 

formation of essential metabolites. Others are toxic. 

MOL YBDENOSIS IN ANIMALS 

The role of copper and molybdenum in certain 

nutritional diseases of livestock is well known and widely 

documented. In animals, molybdenosis results from the 

interactions of copper, molybdenum, sulfide, and sulfate in 

the rumen and tissues of cattle, especially, but also of sheep 

and other ruminants. An excess of molybdenum or sulfate 

in the diet of ruminants interferes with the absorption of the 

metabolically required copper in the gastrointestinal tract. 

Molybdenosis is a worldwide problem occurring not only in 

the United States but also in Canada, Great Britain, New 

Zealand, and the Soviet Union. 

Venugopal and Luckey (1978, p. 255) gave the 

following general symptoms of chronic molybdenum intoxication in animals, "loss of body weight, anorexia, anemia, 

deficient lactation, male sterility owing to testicular degeneration, osteoporosis, and bone-joint abnormalities." Symptoms of acute molybdenum toxicity include severe gastrointestinal irritation and diarrhea, coma, and death from 

cardiac failure. In sheep, "high levels of soil molybdenum 

may induce copper deficiency so that newborn lambs are 

born with defective nervous systems" (Davies, 1985, editorial page). Koval' skii ( 1977) refers to such a nervous 

degeneration as endemic ataxia. If treated early enough, 

molybdenosis is reversible through corrective nutrition. 

Historically, molybdenosis was first recognized in the 

United States in the Central Valley of California and in the 

sinks of southwestern Nevada where cattle and dairy herds 

were difficult, if not impossible, to maintain. Research on 

this problem, therefore, was centered at the University of 

Nevada, Reno. Newly found regions of molybdenum toxicity now extend from the Pacific Northwest to Colorado 

and Wyoming (Kubota, 1975). 

More recently, work by the U.S. Geological Survey 

(USGS) documented incidences of this disease as far east as 

Missouri and farther north into the Dakotas. The Missouri 

incidence was related to contamination of pastures that were 

downstream from an abandoned claypit that overflowed in 

the early 1970's during a prolonged period of heavy rainfall 

(Case and others, 1973; Ebens and others, 1973). At the 

time of the incident, USGS personnel had just completed a 

geochemical survey of the State, and element baselines 

were available to gauge the severity of the geochemical 

changes at the claypit. The ranch (Ranch A) immediately 

adjacent to the claypit received the most severe impact, as 

was seen in the breeding and calving history of the 

beef-cattle herds; calf production was halved in the herd 

affected by the claypit (table 42.1). 

Upon completion of the Missouri project, the U.S. 

Geological Survey began a study of the northern Great 

Plains lignite province. Some preliminary studies that 

compared the geochemical environments of reclaimed surface mines in that region revealed a molybdenosis potential 

at several of the mines (Erdman and others, 1978). As a 

result of that work, I was contacted by the extension agent 

in Harding County, S. Dak., about ranchers' reports of 

problems resembling molybdenosis (poor cow and calf 

performance and some loss of cattle) in cattle in pastures 

around an abandoned uraniferous-lignite strip mine at Flint 

Copper-Molybdenum Imbalances and the Incidence of Nutritional Diseases in Livestock and Humans 179 
Table 42.1. 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-Charo1ais" in 1971 because the sires were changed from Angus to Charo1ais. 

(From Ebens and others, 1973)] 

Herd Sires Dams Cows Calves 

No. Breed Breed Number Age Breed Age Bred Calved Born alive Stillborn 

(yrs) (yrs) Comments 

1 Angus Angus 3 7 Angus 7 54 

2 -do- -do- 1 2 -do- 4 66 

Angus- Charolais 9 Angus 8 54 

2 -do- -do- 5 -do- 5 66 

3 Charolais -do- 4 Charolais 4 24 

Butte. The lignites from the region contain appreciable 

levels of molybdenum, so much so that the pasturage 

adjacent to a former ashing plant in North Dakota, where 

the lignites were burned to concentrate uranium, was found 

to be toxic to cattle (Christianson and Jacobson, 1971). A 

study at Flint Butte (Stone and others, 1983), however, 

showed that the high levels of molybdenum resulted as 

much from lignites that cropped out in the undisturbed 

environment as from those lignites exposed during the 

mining. Stone and others (1983) concluded that, elsewhere 

in the region, naturally occurring release of molybdenum 

into the environment from the uranium-bearing lignites may 

also cause molybdenosis. 

Problems with copper-molybdenum imbalances in 

livestock are far from being resolved in the United States. 

Copper supplementation in molybdic areas designed to 

bring copper to optimum levels relative to the molybdenum 

levels can cause serious side effects (H. Mayland, Agricultural Research Service, Idaho, oral commun., 1986). Salt 

blocks of copper sulfate have been unsuitable because of the 

poor control of their use by livestock. Injections of copper 

glycinate have been used quite widely, but these can cause 

abscesses that affect the marketability of the livestock. 

More recently, a copper chelate has been tried, but incidences of cattle deaths following treatment occurred. 

Imbalances of copper and molybdenum also exist as a 

result of other agricultural practices such as liming and 

clearing woodlands for pastureland. In the Ozarks of 

southern Missouri, for example, bottomland soils are being 

overlimed in an attempt to improve yields of alfalfa and 

clover. According to Dr. Arthur Case, veterinary toxicologist, University of Missouri (written commun., 1986), the 

molybdenum may be at about normal levels, but the copper 

1970 

54 (100) 54 (100) 0 (0) Brought to ranch in 1966. 

36 (54.5) 31 (86.1) 5 (13.9) Brought to ranch Oct. 1969 already 

bred; 7-8 cows rebred. 

1971 

54 (100) 54 (100) 0 (0) One calf died soon after Charolais 

birth. 

24 (36.5) 23 (95.8) 1 (4.2) Undersized dam of stillborn calf 

died soon after calving. 

24 (100) 24 (100) 0 (0) Two cows had difficulty calving, 

but recovered. Artificial insemination, in addition to pasture 

breeding, was used. 

is rendered less available because of the increased soil pH. 

Thus, the copper:molybdenum ratio in the forage is too low 

for cattle, the critical threshold being 2:1. 

MOL YBDENOSIS IN HUMANS 

If some animal diseases, such as molybdenosis, can 

unequivocally be related to the geochemical environment, it 

is logical to seek evidence for similar links in human health. 

As Davies ( 1985) cautioned, establishing a link between 

environmental geochemistry and human health is not easy, 

especially in countries like the United States where food 

production and distribution are so widespread. Incidences 

of molybdenosis in humans have been reported from less 

developed countries, however. 

Construction of a large dam in southern India has 

raised the water table in the surrounding district, making the 

soil more alkaline and thus increasing the molybdenum 

content in sorghum because molybdenum is more mobile in 

an alkaline environment. As sorghum is the dietary staple 

for the local people (Agarwal, 1975), some individuals 

developed genu valgum (knock-knee), a crippling bone 

disease affecting young people (fig. 42.1) that probably 

results from two problems, a molybdenum-induced copper 

deficiency and fluorosis. 

Koval'skii (1977, p. 397-407) described the incidence of endemic gout in Armenia. The inhabitants of the 

Ankavan molybdenum province depend mostly on local 

produce, which contains considerably more molybdenum 

than normal due to soils that are rich in molybdenum but 

deficient in copper. More molybdenum in the diet increases 

the synthesis of the metalloenzyme xanthinoxidase and the 

180 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Figure 42.1. Group of young men showing deformity of 

the knee joint resulting from high dietary intake of molybdenum. This photograph first appeared in New Scientist, 

London (Agarwal, 1975), and is published with their 

permission . 

conversion of xanthine and hypoxanthine into uric acid. 

"Man, unlike animals, apparently lacks the enzyme urate 

oxidase that breaks down uric acid. Consequently, uric acid 

being a relatively insoluble compound, may in some instances be deposited in the tissues of the joints and produce 

symptoms of gout" (Koval 'skii, 1977, p. 190). In a study of 

400 individuals from two settlements in the Ankavan 

province , a direct relation was found between the uric acid 

content in the blood and length of time spent in the 

province . The changes seemed to develop quite rapidly, 

possibly within the first year spent in the area. 

Molybdenum-related nutritional problems in humans 

living in the United States probably do not exist; however, 

to my knowledge, geochemically oriented epidemiological 

studies on human health are extremely rare in this country. 

REFfRENCES CITED 

Agarwal , A.K., 1975, Crippling cost of India's big dam: New 

Scientist, v. 65, p. 260-261. 

Case, A.A ., Selby, L.A. , Hutcheson, D.P., Ebens, R.J., Erdman, 

J.A. , and Feder, G.L. , 1973, Infertility and growth suppression in beef cattle associated with abnormalities in their 

geochemical environment, in Hemphill , D.D., ed. , Trace 

substances in environmental health- VI, Proceedings of 

University of Missouri's 6th annual conference on trace 

substances in environmental health, June 13-15, 1972: 

Columbia, Mo., University of Missouri , p. 15-21. 

Christianson, G.A., and Jacobson , G.A., 1971 , Report on molybdenosis in farm animals and its relation to a uraniferous 

lignite ashing plant: Unpublished report, available from 

North Dakota State Department of Health, Environmental 

Health and Engineering Service, Bismarck, N. Dak. 

Davies, B.E., 1985, Airs, waters, and places: Environmental 

Geochemistry and Health, v. 7, editorial page. 

Ebens, R.J., Erdman, J.A., Feder, G.L., Case, A.A., and Selby, 

L.A., 1973, Geochemical anomalies of a claypit area, 

Callaway County, Mo. , and related metabolic imbalance in 

beef cattle: U.S. Geological Survey Professional Paper 

807 , 24 p. 

Erdman, J.A., Ebens, R.J. , and Case, A.A. , 1978 , Molybdenosis-A potential problem in ruminants ranging over coalmine spoils: Journal of Range Management, v. 31 , 

p. 34-36. 

Koval'skii, V.V., 1977, Geochimicheskaya ekologia [Geochemical ecology]: Ottawa , Department of the Secretary of 

State, Translation Bureau, Multilingual Services Division, 

579 p. 

Kubota, J., 1975, Areas of molybdenum toxicity to grazing 

animals in the Western United States: Journal of Range 

Management, v. 28 , p. 252-256. 

Stone, L.R., Erdman , J.A ., Feder, G.L., and Holland, H.D., 

1983, Molybdenosis in an area underlain by uraniumbearing lignites in the northern Great Plains: Journal of 

Range Management, v. 36, p. 280-285. 

Venugopal, B., and Luckey , T.D. , 1978, Metal toxicity in 

mammals, v. 2 of Chemical toxicity of metals and metalloids: New York, Plenum Press, 409 p. 

Copper-Molybdenum Imbalances and the Incidence of Nutritional Diseases in livestock and Humans 181 

43. Bibliography of Selected Geochemical 

Studies of the Environment by the 

U.S. Geological Survey 

Compiled by Hansford T. Shacklette, R.C. Severson, and Larry P. Gough 

[Locations of numbered studies that can be areally 

plotted are shown on figures 43. 1-43 .4] 

I. GEOCHEMICAL STUDIES OF THE BROADEST 

SCALE (FIG. 43.1) 

Study No. la. Soil Geochemistry East and West of the 

97th Meridian, Conterminous United States (fig. 43.1). 

Boerngen. J. G., and Shacklette, H. T., 1981, Chemical analyses 

of soils and other surficial materials of the conterminous 

United States: U.S. Geological Survey Open-File Report 

81-197. 145 p. 

Shacklette, H. T., 1975, Surficial materials in the conterminous 

United States (study no. 21 ), in Connor. J.J., and Shacklette, H. T., 1975. Background geochemistry of some 

rocks, soils, plants, and vegetables in the conterminous 

United States: U.S. Geological Survey Professional Paper 

574-F, p. F9. 

Shacklette, H.T., and Boerngen, J.G., 1984, Element concentrations in soils and other surficial materials of the conterminous United States: U.S. Geological Survey Professional 

Paper 1270, 105 p. 

Shacklette, H.T., Boerngen, J.G., Cahill, J.P., and Rahill, R.L., 

1973, Lithium in surficial materials of the conterminous 

United States and partial data on cadmium: U.S. Geological 

Survey Circular 673, 8 p. 

Shacklette, H.T., Boerngen. J.G., and Keith. J.R., 1974, Selenium, fluorine, and arsenic in surficial materials of the 

conterminous United States: U.S. Geological Survey Circular 692, 14 p. 

Shacklette, H.T., Boerngen, J.G., and Turner, R.L., 1971, 

Mercury in the environment-Surficial materials of the 

conterminous United States: U.S. Geological Survey Circular 644. 5 p. 

Shacklette, H.T., Hamilton, J.C., Boerngen, J.G .. and Bowles, 

J .M .. 1971, Elemental composition of surficial materials in 

the conterminous United States: U.S. Geological Survey 

Professional Paper 574-D, 71 p. 

Study No. lb. Chemical Data for Elements in Water at 

Selected Locations. 

Anderson, B.M., 1971, Calcium-carbonate hardness in public 

water supplies in the conterminous United States, in Environmental geochemistry of health and disease: Geological 

Society of America Memoir 123, p. 151-153. 

---1972, Lithium in surface and ground waters of the conterminous United States: U.S. Geological Survey Open-File 

Report 72-0006, 7 p. 

Fleischer. Michael, 1962, Fluoride content of ground water in the 

conterminous United States (maximum reported value for 

each county): U.S. Geological Survey Miscellaneous Geologic Investigations Map I-387, scale 1:5,000,000. 

Study No. lc. Geochemical Studies of the Western 

Energy Region, Northern Great Plains, and Parts of the 

Rocky Mountains (fig. 43.1). 

Askenasy, P.E., and Severson, 1988, Chemical procedures applicable to overburden and mine soil, chap. 4, in Hossner, 

L.R., ed., Reclamation of surface-mined lands, v. 1: Boca 

Raton, Fla .. CRC Press, p. 55-80. 

Connor, J .J., 1975, Surface soils and sagebrush, Wyoming and 

Montana (study no. 35), in Connor, J.J., and Shacklette, 

H.T., Background geochemistry of some rocks, soils, 

plants, and vegetables in the conterminous United States: 

U.S. Geological Survey Professional Paper 574-F, p. 

FlOO. 

---1982, The need for experimental design in trace element 

geochemistry [abs.], in Gough, L.P., and Severson, R.C., 

eds., Trace-element mobilization in western energy regions 

-Proceedings of a symposium held November 21-24, 

1982, in Denver, Colorado: Golden, Colo., Colorado 

School of Mines Research Institute Press. p. 2. 

Crock, J.G., and Severson, R.C., 1980, Four reference soil and 

rock samples for measuring element availability in the 

western energy regions: U.S. Geological Survey Circular 

841, 16 p. 

Bibliography of Selected Geochemical Studies of the Environment by the U.S. Geological Survey 183 
45° 

35° 

30° 

25° 

1W 110° 105° 100° 

g5o goo 85° 80° 

500 MILES 

f--.--'--1 .-, -,,-1-1 ---.-, __.,,,r---'----'' 

500 KILOMETERS 

g5o goo 85° 

75° 70° 65° 

45° 

40° 

35° 

30° 

25° 

80° 75° 

Figure 43.1. Geochemical studies of the broadest scale in the conterminous United States. 1a, Soil geochemistry east and 

west of the 97th meridian; 1c, Geochemical studies of the western energy region, northern Great Plains, and parts of the 

Rocky Mountains. 

Ebens, R.J., and McNeal, J.M., 1982, Shale and sandstone of the 

Fort Union Formation in the northern Great Plains (study 

no. 1), in Ebens, R.J., and Shacklette, H.T., Geochemistry 

of some rocks, mine spoils, stream sediments, soils, plants, 

and waters in the western energy region of the conterminous United States: U.S. Geological Survey Professional 

Paper 1237 p. 4. 

Erdman, J.A., and Gough, L.P., 1982, Miscellaneous small 

grains from the northern Great Plains (study no. 21), in 

Ebens, R.J., and Shacklette, H.T., Geochemistry of some 

rocks, mine spoils, stream sediments, soils, plants, and 

waters in the western energy region of the conterminous 

United States: U.S. Geological Survey Professional Paper 

1237' p. 19. 

Feder, G.L., 1982, Ground water chemistry, Poplar River basin, 

Montana and Saskatchewan (study no. 27), in Ebens, R.J., 

and Shacklette, H.T., Geochemistry of some rocks, mine 

spoils, stream sediments, soils, plants, and waters in the 

western energy region of the conterminous United States: 

U.S. Geological Survey Professional Paper 1237, p. 24. 

Gough, L.P., McNeal, J.M., and Severson, R.C., 1980, Predicting native plant copper, iron, manganese, and zinc levels 

using DTPA and EDTA soil extractants, northern Great 

Plains: Soil Science Society of America Journal, v. 44, no. 

5, p. 1030-1036. 

Gough, L.P., and Severson, R.C., 1981, Trace metal toxicity 

assessment at 11 Western United States surface coal mines 

[abs.]: Madison, Wise., American Society of Agronomy, 

Agronomy Abstracts, p. 26. 

---1982, Trace element mobilization in western energy 

regions-Proceedings of a symposium held November 

21-24, 1982, in Denver, Colorado: Golden, Colo., Colorado School of Mines Research Institute Press, 50 p. 

---1983, Rehabilitation materials from surface coal mines in 

Western U.S.A., pt. II, Biogeochemistry of wheatgrass, 

alfalfa, and fourwing saltbush: Reclamation and Revegetation Research, v. 2, p. 103-122. 

Gough, L.P., Severson, R.C., and McNeal, J.M., 1982, Soils and 

native plants, northern Great Plains (study no. 18), in 

Ebens, R.J .. and Shacklette, H.T., Geochemistry of some 

rocks, mine spoils, stream sediments, soils, plants, and 

waters in the western energy region of the conterminous 

United States: U.S. Geological Survey Professional Paper 

1237, p. 16-17. 

184 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Herring, J.R., Hinkley, T.K., and Ebens, R.J., 1982, Geochemistry of sandstones from the Fort Union Formation, northern Great Plains (study no. 4), in Ebens, R.J., and 

Shacklette, H.T., Geochemistry of some rocks, mine 

spoils, stream sediments, soils, plants, and waters in the 

western energy region of the conterminous United States: 

U.S. Geological Survey Professional Paper 1237, p. 6. 

Hinkley, T.K., and Ebens, R.J., 1982, Geochemistry of finegrained rocks in cores of the Fort Union Formation (study 

no. 3), in Ebens, R.J., and Shacklette, H.T., Geochemistry 

of some rocks, mine spoils, stream sediments, soils, plants, 

and waters in the western energy region of the conterminous United States: U.S. Geological Survey Professional 

Paper 1237, p. 6. 

Jackson, L.L., Engleman, E. E., and Severson, R.C., 1985, 

Characterization of the forms of sulfur in overburden 

materials of the Western United States, in Proceedings, 2d 

annual meeting of the American Society of Surface Mining 

and Reclamation, Denver, Colo., October 8-10, 1985: 

Princeton, W. Va., American Society for Surface Mining 

and Reclamation, p. 49a-49d. 

McNeal, J.M., 1982, Stream-sediment chemistry in the northern 

Great Plains (study no. 6), in Ebens, R.J., and Shacklette, 

H. T., Geochemistry of some rocks, mine spoils, stream 

sediments, soils, plants, and waters in the western energy 

region of the conterminous United States: U.S. Geological 

Survey Professional Paper 1237, p. 9. 

---1985, The occurrence of extractable elements in soils from 

the northern Great Plains: Soil Science Society of America 

Journal, v. 49, p. 873-881. 

McNeal, J.M., Lee, D.E., and Millard, H.T., Jr., 1981, The 

distribution of uranium and thorium in granitic rocks of the 

Basin and Range province, Western United States: Journal 

of Geochemical Exploration, v. 14, no. 1, p. 25-40. 

Miesch, A.T., 1975, Sandstone, shale, and carbonate rocks of the 

Sauk sequence of Precambrian, Cambrian, and Ordovician 

age on the cratonic part of the Western United States (study 

no. 3), in Connor, J.J., and Shacklette, H.T., Background 

geochemistry of some rocks, soils, plants, and vegetables 

in the conterminous United States: U.S. Geological Survey 

Professional Paper 574-F, p. F3-F6. 

Severson, R.C., and Fisher, S.E., Jr., 1985a, Results of the 1st 

Western Task Force Round Robin Soil and Overburden 

Analysis Program: U.S. Geological Survey Open-File 

Report 85-220, 58 p. 

---1985b, Western soil and overburden task force group 

round robin analyses in 1984-1985. in Proceedings, 2d 

annual meeting of the American Society for Surface Mining 

and Reclamation. Denver, Colo., October 8-10, 1985: 

Princeton, W. Va., American Society for Surface Mining 

and Reclamation. p. 90a-90c. 

---1986, Results of the 2d Western Task Force Round Robin 

Soil and Overburden Analysis Program: U.S. Geological 

Survey Open-File Report 86-49, 30 p. 

Severson, R.C., and Gough, L.P., 1983a, Rehabilitation materials 

from surface coal mines in Western U.S.A., pt. I, Chemical characteristics of spoil and replaced cover-soil: Reclamation and Revegetation Research, v. 2, p. 83-102. 

---1983b, Boron in mine soils and rehabilitation plant species 

at selected surface coal mines in Western United States: 

Journal of Environmental Quality, v. 12, p. 142-146. 

---1984, Rehabilitation materials from surface-coal mines in 

Western U.S.A., pt. III, Relations between elements in 

mine soil and uptake by plants: Reclamation and Revegetation Research, v. 3, p. 185-197. 

Severson, R.C., Gough, L.P., and McNeal, J.M., 1977, Availability of elements in soils to native plants, northern Great 

Plains: U.S. Geological Survey Open-File Report 77-847, 

93 p. 

Severson, R.C., and Tidball, R.R., 1979, Spatial variation in total 

element concentration in soil within the northern Great 

Plains coal region: U.S. Geological Survey Professional 

Paper 1134-A, 18 p. 

---1982, Total soil chemistry, northern Great Plains (study 

no. 16), in Ebens, R.J., and Shacklette, H.T., Geochemistry of some rocks, mine spoils, stream sediments, soils, 

plants, and waters in the western energy region of the 

conterminous United States: U.S. Geological Survey Professional Paper 1237, p.16. 

Shultz, L.G., Tourtelot, H.A., Gill, J.R., and Boerngen, J.G., 

1980, Composition and properties of the Pierre Shale and 

equivalent rocks, northern Great Plains region: U.S. Geological Survey Professional Paper 1064-B, 114 p. 

Tidball, R.R., 1978, Chemical and mineralogical evaluation of 

soils, Hanging Woman Creek EMRIA site, Big Horn 

County, Montana: U.S. Geological Survey Open-File 

Report 78-346, 88 p. 

Vine, J.D., and Tourtelot, E.B., 1973, Geochemistry of lower 

Eocene sandstones in the Rocky Mountain region: U.S. 

Geological Survey Professional Paper 789, 36 p. 

Area No. 2. Soil and Plant Geochemistry, Alaska 

(fig. 43.2). 

Gough, L.P., Peard, J.L., Severson, R.C., Shacklette, H.T., 

Tompkins, M.L., Stewart, K.C., and Briggs, P.H., 1984, 

Chemical analyses of soils and other surficial materials, 

Alaska: U.S. Geological Survey Open-File Report 84-423, 

79 p. 

Gough, L.P., and Severson, R.C., 1981, Element concentrations 

in rehabilitation species from thirteen coal-strip mines in 

the five Western States and Alaska: U.S. Geological 

Survey Open-File Report 81-182, 118 p. 

Gough, L.P., Severson, R.C., and Shacklette, H.T., 1988, 

Element concentration in soils and other surficial materials 

in Alaska: U.S. Geological Survey Professional Paper 

1458, 53 p. 

Severson, R.C., and Gough, L.P., 1983, Chemical composition 

and variability of soils from the Capps coal field, Alaska: 

U.S. Geological Survey Open-File Report 83-190, 36 p. 

---1984, Estimated physiological tolerance ranges for 

selected elements in soils, Capps coal field, in Reed, K.M., 

and Bartsch-Winkler, Susan, eds., The United States Geological Survey in Alaska; accomplishments during 1982: 

U.S. Geological Survey Circular 939, p. 75-78. 

Bibliography of Selected Geochemical Studies of the Environment by the U.S. Geological Survey 185 
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12w! 

178° 180° 178° 172° ln·~~·1o''F.J'11oJ.: I I I 105., \I 122 ~93 ..... 

cq ALEUTIAN ISLANDS ~07 124 r· 106 ;;. o..o 0 0 ~...8~ ... ~8. ·;· 

0 300 600 KILOMETERS I I I I I I I I I I 

0 1 00 200 300 MILES 

Figure 43.2. Geochemical studies of the broadest scale in Alaska. Map shows studies of soil and plant geochemistry in Alaska. Numbers 

refer to studies listed in Gough and others (1988). 
125" 120" 115" 110" 105° 100" S5" so· S5" so· 75" 70" 65" 

45" 45° 

40" 

35" 35" 

30" 30~ 

25° 500 MILES 

II II I II I 25" 

500 KILOMETERS 

110° 105" 100" S5" so· S5" so· 75" 

Figure 43.3. Locations of numbered regional geochemical studies (3-14) of rocks, stream sediments, soils, plants, and 

waters. 

II. REGIONAL GEOCHEMICAL STUDIES OF 

ROCKS, STREAM SEDIMENTS, SOILS, PLANTS, 

AND WATERS (FIG. 43.3). 

Study No. 3. California Stream Sediments. 

McNeal, J.M., 1985, Regional-scale geochemical mapping in the 

United States, in Thornton, lain, ed. , Proceedings of the 1st 

International Symposium on Geochemistry and Health, 

April 16-17, 1985, London, England: London, Science 

Reviews, Ltd., Monograph Series, Environmental Geochemistry and Health, p. 16-30. 

McNeal, J.M., and Miller, W.R., 1982, Regional geochemical 

mapping of the Southern Coast Ranges, California, using 

stream sediments and heavy-mineral concentrates [abs.], in 

Program with Abstracts, Ninth International Geochemical 

Exploration Symposium, Saskatoon, Saskatchewan, Canada: Ontario, Canada, Association of Exploration 

Geochemists, p. 116-117. 

McNeal, J.M., Miller, W.R., and Motooka, J.M., 1982, Geochemical mapping of the distribution of elements in stream 

sediments, Southern Coast Ranges, California [abs.]: Geological Society of America, Abstracts with Programs, v. 

14, no. 4, p. 214. 

Study No. 4. Elements in Big Sagebrush. 

Connor, J.J., Keith, J.R., and Anderson, B.M., 1982, Tracemetal variation in soils and sagebrush in the Powder River 

Basin, Wyoming and Montana (study no. 20), in Ebens, 

R.J., and Shacklette, H.T., Geochemistry of some rocks, 

mine spoils, stream sediments, soils, plants, and waters in 

the western energy region of the conterminous United 

States: U.S. Geological Survey Professional Paper 1237, 

p. 17-19. 

Erdman, J.A., and Harrach, G.H., 1981, Uranium in big sagebrush from Western U.S. and evidence of possible mineralization in the Owyhee Mountains of Idaho: Journal of 

Geochemical Exploration, v. 14, no. 1, p. 83-94. 

Gough, L.P., and Erdman, J.A., 1982, Big sagebrush from eight 

western physiographic provinces (study no. 23), in Ebens, 

R.J., and Shacklette, H.T., Geochemistry of some rocks, 

mine spoils, stream sediments, soils, plants, and waters in 

the western energy region of the conterminous United 

States: U.S. Geological Survey Professional Paper 1237, 

p. 21. 

---1983, Baseline elemental concentrations for big sagebrush 

from Western U.S.A.: Journal of Range Management, 

v. 36, no 6, p. 718-722. 

Bibliography of Selected Geochemical Studies of the Environment by the U.S. Geological Survey 187 
Area No.5. Fort Union Region. 

Ebens, R .J., and McNeal, J .M., 1982, Shale and sandstone of the 

Fort Union Formation in the northern Great Plains (study 

no. 1), in Ebens, R.J., and Shacklette, H.T., Geochemistry 

of some rocks, mine spoils, stream sediments, soils, plants, 

and waters in the western energy region of the conterminous United States: U.S. Geological Survey Professional 

Paper 1237, p. 4. 

Feder, G.L., 1982, Ground-water chemistry, Fort Union coal 

region (study no. 25), in Ebens. R.J .. and Shacklette, 

H. T., Geochemistry of some rocks, mine spoils, stream 

sediments' soils' plants' and waters in the western energy 

region of the conterminous United States: U.S. Geological 

Survey Professional Paper 1237, p. 21. 

Herring, J.R., Hinkley, T.K., and Ebens, R.J., 1982, Geochemistry of sandstones from the Fort Union Formation, Northern Great Plains (study no. 4), in Ebens, R.J., and 

Shacklette, H. T., Geochemistry of some rocks, mine 

spoils, stream sediments, soils, plants, and waters in the 

western energy region of the conterminous United States: 

U.S. Geological Survey Professional Paper 1237, p. 6. 

Hinkley, T.K., and Ebens, R.J., 1982a, Geochemistry of finegrained rocks in cores of the Fort Union Formation (study 

no. 3). in Ebens, R.J., and Shacklette, H.T., Geochemistry 

of some rocks, mine spoils, stream sediments, soils, plants, 

and waters in the western energy region of the conterminous United States: U.S. Geological Survey Professional 

Paper 1237, p. 6. 

---1982b, Chemical and mineralogical analyses of core samples from Hanging Woman Creek, Montana (study no. 2), 

in Ebens, R.J., and Shacklette, H.T., Geochemistry of 

some rocks, mine spoils, stream sediments, soils, plants, 

and waters in the western energy region of the conterminous United States: U.S. Geological Survey Professional 

Paper 1237, p. 6. 

Tidball, R.R., 1982, Chemical and mineralogical evaluation of 

soils, Hanging Woman Creek, Montana (study no. 14) in 

Ebens, R.J., and Shacklette, H.T., Geochemistry of some 

rocks, mine spoils, stream sediments, soils, plants, and 

waters in the western energy region of the conterminous 

United States: U.S. Geological Survey Professional Paper 

1237' p. 13-14. 

Area No.6. Powder River Region. 

Anderson, B.M., Keith, J.R., and Connor, J.J., 1975, Antimony, 

arsenic, germanium, lithium, mercury, selenium, tin, and 

zinc in soils of the Powder River Basin. in Geochemical 

survey of the western coal regions, 2d annual progress 

report, July 1975: U.S. Geological Survey Open-File 

Report 75---436. p. 50-57. 

Connor. J.J .. Denson, N.M., and Hamilton, J.C., 1976, Geochemical discrimination of sandstones of the basal Wasatch 

Formation, Powder River Basin, Wyoming and Montana, 

in Laudon, R.B., ed., Geology and energy resources of the 

Powder River; Wyoming Geological Association, 28th 

annual field conference guidebook: Casper, Wyoming Geological Association, p. 291-297. 

Connor, J.J., Keith, J.R., and Anderson, B.M., 1976, Tracemetal variation in soils and sagebrush in the Powder River 

Basin, Wyoming and Montana: U.S. Geological Survey 

Journal of Research, v. 4, no. 1, p. 49-59. 

---1982, Trace-metal variation in soils and sagebrush in the 

Powder River Basin, Wyoming and Montana (study no. 

20), in Ebens, R.J., and Shacklette, H.T., Geochemistry of 

some rocks, mine spoils, stream sediments, soils, plants, 

and waters in the western energy region of the conterminous United States: U.S. Geological Survey Professional 

Paper 1237, p. 17-19. 

Erdman, J.A., and Gough, L.P., 1982, Soil lichens from the 

Powder River Basin (study no. 22), in Ebens, R.J., and 

Shacklette, H.T., Geochemistry of some rocks, mine 

spoils, stream sediments, soils, plants, and waters in the 

western energy region of the conterminous United States: 

U.S. Geological Survey Professional Paper 123 7, 

p. 19-21. 

Feder, G .L., 1982, Ground-water chemistry, Powder River coal 

region, Montana and Wyoming (study no. 28), in Ebens, 

R.I., and Shacklette, H.T., Geochemistry of some rocks, 

mine spoils, stream sediments, soils, plants, and waters in 

the western energy region of the conterminous United 

States: U.S. Geological Survey Professional Paper 1237, 

p. 24. 

Keith, J.R., Anderson, B.M., and Connor, J.J., 1974, Tracemetal variation in the Powder River Basin, in Geochemical 

survey of the western coal region, 1st annual progress 

report, July 1974: U.S. Geological Survey Open-File 

Report 74-250, p. 14-29. 

McNeal, J.M., Keith, J.R., Anderson, B.M., and Boerngen, 

J.G., 1982, Chemistry of Powder River sediments (study 

no. 7), in Ebens, R.J., and Shacklette, H.T., Geochemistry 

of some rocks, mine spoils, stream sediments, soils, plants, 

and waters in the western energy region of the conterminous United States: U.S. Geological Survey Professional 

Paper 1237, p. 9. 

Tidball, R.R., 1975, Sampling requirements for mapping soil 

geochemistry in the Powder River Basin, MontanaWyoming, in Geochemical survey of the western coal 

region, 2d annual progress report, July 1975: U.S. Geological Survey Open-File Report 75---436, p. 20-28. 

Tidball, R.R., and Ebens, R.J., 1976, Regional geochemical 

baselines in soils of the Powder River Basin, MontanaWyoming, in Laudon, R.B., ed., Geology and energy 

resources of the Powder River; Wyoming Geological Association, 28th annual field conference guidebook: Casper, 

Wyoming Geological Association, p. 299-310. 

---1982, Soils of the Powder River Basin, Wyoming and 

Montana (study no. 13), in Ebens, R.J., and Shacklette, 

H.T., Geochemistry of some rocks, mine spoils, stream 

sediments, soils, plants, and waters in the western energy 

region of the conterminous United States: U.S. Geological 

Survey Professional Paper 1237, p. 13. 

Tidball, R.R., Erdman, J.A., and Ebens, R.J., 1975, Geochemical baselines for sagebrush and soil, Powder River Basin, 

Montana-Wyoming, in U.S. Geological Survey, Geochemical survey of the western coal regions, 1st annual progress 

report, July 1974: U.S. Geological Survey Open-File 

Report 74-250, p. 6-13. 

188 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Area No. 7. Bighorn River Region. 

Severson, R.C., 1979, Regional soil chemistry in the Bighorn and 

Wind River Basins, Wyoming and Montana: U.S. Geological Survey Professional Paper 1134-B, 9 p. 

---1982. Soil geochemistry of the Wind River and Big Horn 

Basins, Wyoming and Montana (study no. 17), in Ebens, 

R.J., and Shacklette, H.T., Geochemistry of some rocks, 

mine spoils, stream sediments, soils, plants, and waters in 

the western energy region of the conterminous United 

States: U.S. Geological Survey Professional Paper 1237, 

p. 16. 

Area No. 8. Wind River Region. 

Severson, R.C., 1979. Regional soil chemistry in the Bighorn and 

Wind River Basins, Wyoming and Montana: U.S. Geological Survey Professional Paper 1134-B, 9 p. 

---1982, Soil geochemistry of the Wind River and Big Horn 

Basins, Wyoming and Montana (study no. 17), in Ebens, 

R.J., and Shacklette, H.T., Geochemistry of some rocks, 

mine spoils, stream sediments, soils, plants, and waters in 

the western energy region of the conterminous United 

States: U.S. Geological Survey Professional Paper 1237, 

p. 16. 

Area No. 9. Uinta-Piceance Region. 

Anderson, B.M., 1982a, Effects of processed oil shale on the 

element content of Atriplex canescens: U.S. Geological 

Survey Open-File Report 82-1051, 18 p. 

---1982b. Trace element content of Atriplex canescens from 

the Colorado State University oil shale revegetation plot, 

Piceance Basin, Colorado [abs.], in Gough, L.P., and 

Severson, eds., Trace element mobilization in western 

energy regions-Proceedings of a symposium held November 21-24, 1982, Denver, Colorado: Golden, Colo., Colorado School of Mines Research Institute Press, p. 40. 

Dean, W.E., 1982, Geochemistry of an oil shale core, Piceance 

Creek Basin, Colorado (study no. 5), in Ebens, R.J., and 

Shacklette, H.T., Geochemistry of some rocks, mine 

spoils, stream sediments, soils, plants, and waters in the 

western energy region of the conterminous United States: 

U.S. Geological Survey Professional Paper 1237, p. 6-9. 

Dean, W.E., Ringrose, C.D., and Klusman, R.W., 1982, Soils of 

the Piceance Creek Basin, western Colorado (study no. 15), 

in Ebens, R.J., and Shacklette, H.T., Geochemistry of 

some rocks, mine spoils, stream sediments, soils, plants, 

and waters in the western energy region of the conterminous United States: U.S. Geological Survey Professional 

Paper 1237, p. 14-16. 

McNeal, J .M., and Feder, G.L., 1982, Stream-sediment chemistry of the Uinta and Piceance Creek Basins, Utah and 

Colorado (study no. 8), in Ebens, R.J., and Shacklette, 

H. T. , Geochemistry of some rocks, mine spoils, stream 

sediments, soils, plants, and waters in the western energy 

region of the conterminous United States: U.S. Geological 

Survey Professional Paper 1237, p. 11. 

McNeal, J.M., Ringrose, C.D., and Klusman, R.W., 1982, 

Geochemical variability of sediments from two streams in 

the Piceance Creek Basin, Colorado (study no. 9), in 

Ebens, R.J., and Shacklette, H.T., Geochemistry of some 

rocks, mine spoils, stream sediments, soils, plants, and 

waters in the western energy region of the conterminous 

United States: U.S. Geological Survey Professional Paper 

1237, p. 11. 

Tidball, R.R., and Severson, R.C., 1977, Chemical variation in 

alluvial soils in the oil shale region, in Geochemical survey 

of the western energy regions, fourth annual progress 

report, July 1977: U.S. Geological Survey Open-File 

Report 77-872, p. 55_:64. 

---1982, Alluvial soils of the Piceance Creek and Uinta 

Basins (study no. 12), in Ebens, R.J., and Shacklette, 

H.T., Geochemistry of some rocks, mine spoils, stream 

sediments, soils, plants, and waters in the western energy 

region of the conterminous United States: U.S. Geological 

Survey Professional Paper 1237, p. 13. 

Tuttle, M.L., Ackerman, D.J., Dean, W.E., Briggs, P.H., and 

Bartel, A.N., 1983, Chemical and mineral composition 

data on oil shale and reported oil-shale wastes from 

Rulison, Colorado: U.S. Geological Survey Open-File 

Report 83-378, 32 p. 

Tuttle, M.L., Dean, W.E., and Ackerman, D.J., 1985, An 

evaluation of the effects of weathering on a 50-year old 

reported oil-shale waste pile, Rulison experimental report, 

Colorado, in Gary, J .H., ed., Eighteenth Oil Shale Symposium Proceedings: Golden, Colo., Colorado School of 

Mines Press, p. 338-346. 

Tuttle, M.L., Severson, R.C., Dean, W.E., and Klusman, R.W., 

1986, Geochemical variability of soils and biogeochemical 

variability of plants in the Piceance Basin, Colorado, in 

Geochemical survey of the western energy regions: U.S. 

Geological Survey Professional Paper 1134-E, 46 p. 

Area No. 10. San Juan Basin Region-Rock, Soil, and 

Plant Chemistry. 

Gough, L.P., and Severson, R.C., 1981, Biogeochemical variability of plants at native and altered sites, San Juan Basin, 

New Mexico, in Geochemical survey of the western energy 

regions: U.S. Geological Survey Professional Paper 

1134-D, 26 p. 

Hinkley, T.K., Herring, J.R., Smith, K.S., and Boerngen, J.G., 

1980, Overburden geochemistry of the U.S. Bureau of 

Land Management experimental coal mining reclamation 

site at Ojo Encino, northeast McKinley County, San Juan 

Basin, New Mexico: U.S. Geological Survey Open-File 

Report 80-1226, 21 p. 

Severson, R.C., and Gough, L.P., 1981, Geochemical variability 

of natural soils and reclaimed mine spoil soils in the San 

Juan Basin, in Geochemical survey of the western energy 

regions: U.S. Geological Survey Professional Paper 

1134-C, 39 p. 

Bibliography of Selected Geochemical Studies of the Environment by the U.S. Geological Survey 189 
Study No. 11. Missouri Geochemical Studies. 

Connor, J.J., 1975a, Sandstone and carbonate rocks of the Sauk 

sequence of Cambrian and Ordovician age in Missouri and 

northern Arkansas (study no. 4), in Connor, J.J., and 

Shacklette, H. T., Background geochemistry of some rocks, 

soils, plants, and vegetables in the conterminous United 

States: U.S. Geological Survey Professional Paper 574-F, 

p. F4. 

---1975b, Sandstone, shale, and limestone of Pennsylvanian 

age in Missouri, Kansas, and Oklahoma (study no. 6), in 

Connor, J.J., and Shacklette. H.T., Background geochemistry of some rocks, soils, plants, and vegetables in the 

conterminous United States: U.S. Geological Survey Professional Paper 574--F, p. F6. 

---1975c, Limestone of the Tippecanoe sequence of Ordovician, Silurian, and Devonian ages in Missouri (study no. 

10), in Connor. J.J., and Shacklette, H.T., Background 

geochemistry of some rocks, soils, plants, and vegetables 

in the conterminous United States: U.S. Geological Survey 

Professional Paper 574-F, p. F7. 

---1975d, Quaternary loess in Missouri (study no. 13), in 

Connor, J.J., and Shacklette, H.T., Background geochemistry of some rocks, soils, plants, and vegetables in the 

conterminous United States: U.S. Geological Survey Professional Paper 574--F, p. F8. 

Connor, J.J., and Ebens, R.J., 1980, Geochemistry of bedrock 

units in Missouri and parts of adjacent States: U.S. Geological Survey Professional Paper 954--F, 55 p. 

Ebens, R.J., 1975a, Granitic rocks of Precambrian age in the St. 

Francois Mountains, Missouri (study no. 1 ), in Connor, 

J.J., and Shacklette, H.T., Background geochemistry of 

some rocks, soils, plants, and vegetables in the conterminous United States: U.S. Geological Survey Professional 

Paper 574-F, p. F3. 

---1975b, Residuum on carbonate rocks of Cambrian, Ordovician, and Mississippian ages in southern Missouri and 

northern Arkansas (study no. 12), in Connor, J.J., and 

Shacklette, H. T., Background geochemistry of some rocks, 

soils, plants, and vegetables in the conterminous United 

States: U.S. Geological Survey Professional Paper 574-F, 

p. F8. 

Ebens, R.J., and Connor. J.J., 1980, Geochemistry of loess and 

carbonate residuum: U.S. Geological Survey Professional 

Paper 954--G, 32 p. 

Erdman J.A., 1975a, Native vegetation and uncultivated soils in 

Missouri (study no. 20), in Connor, J .J., and Shacklette, 

H.T., Background geochemistry of some rocks, soils, 

plants, and vegetables in the conterminous United. States: 

U.S. Geological Survey Professional Paper 574-F, p. F9. 

---1975b, Cedar in Missouri (study no .. 24), in Connor, J.J., 

and Shacklette, H.T., Background geochemistry of some 

rocks, soils, plants, and vegetables in the conterminous 

United States: U.S. Geological Survey Professional Paper 

574-F, p. FlO. 

Erdman, J.A., Shacklette, H.T., and Keith, J.R., 1976a, Elemental composition of selected native plants and associated 

soils from major vegetation-type areas in Missouri: U.S. 

Geological Survey Professional Paper 954-C, 87 p. 

---1976b, Elemental composition of com grains, soybean 

seed, pasture grasses, and associated soils from selected 

areas in Missouri: U.S. Geological Survey Professional 

Paper 954-D, 23 p. 

Feder, G.L., 1982, Geochemical survey of waters of Missouri: 

U.S. Geological Survey Professional Paper 954--E, 77 p. 

Shacklette, H.T., 1975, Crop plants and associated soils in 

Missouri (study no. 17), in Connor, J .J., and Shacklette, 

H.T., Background geochemistry of some rocks, soils, 

plants, and vegetables in the conterminous United States: 

U.S. Geological Survey Professional Paper 574-F, p. F8. 

Tidball, R.R., 1975, Agricultural soils in Missouri (study no. 16), 

in Connor, J.J., and Shacklette, H.T., Background geochemistry of some rocks, soils, plants, and vegetables in 

the conterminous United States: U.S. Geological Survey 

Professional Paper 574-F, p. F8. 

---1976, Chemical variation of soils in Missouri associated 

with selected levels of the soil classification system: U.S. 

Geological Survey Professional Paper 954--B, 16 p. 

---1984a, Geography of soil geochemistry of Missouri agricultural soils: U.S. Geological Survey Professional Paper 

954-H, 54 p. 

---1984b, Geochemical classification by factor analysis of 

Missouri agricultural soils: U.S. Geological Survey Professional Paper 954-I, 19 p. 

Study No. 12. Kentucky Rocks, Soils, and Plants. 

Connor, J.J., 1975a, Sandstone, shale, and carbonate rocks of 

Paleozoic age in Kentucky (study no. 5), in Connor, J.J., 

and Shacklette, H. T., Background geochemistry of some 

rocks, soils, plants, and vegetables in the conterminous 

United States: U.S. Geological Survey Professional Paper 

574-F, p. F6. 

---1975b, Shale of early Mississippian age in Kentucky 

(study no. 8), in Connor, J.J., and Shacklette, H.T., 

Background geochemistry of some rocks, soils, plants, and 

vegetables in the conterminous United States: U.S. Geological Survey Professional Paper 574-F, p. F7. 

---1975c, Black shale of Devonian and Mississippian age in 

Kentucky (study no. 9), in Connor, J.J., and Shacklette, 

H.T., Background geochemistry of some rocks, soils, 

plants, and vegetables in the conterminous United States: 

U.S. Geological Survey Professional Paper 574--F, p. F7. 

---1975d, Sideritic rocks of Mississippian and Pennsylvanian 

age in Kentucky (study no. 11), in Connor, J.J., and 

Shacklette, H.T., Background geochemistry of some rocks, 

soils, plants, and vegetables in the conterminous United 

States: U.S. Geological Survey Professional Paper 574--F, 

p. F7. 

---198la, Geochemical analyses and summaries of carbonate 

rocks from Kentucky: U.S. Geological Survey Open-File 

Report 81-509, 121 p. 

---1981b, Geochemical analyses and summaries of Mississippian and Pennsylvanian sandstones from Kentucky: U.S. 

Geological Survey Open-File Report 81-1098, 91 p. 

---1981c, Geochemical analyses and summaries of shale from 

Kentucky: U.S. Geological Survey Open-File Report 

81-1097, 116 p. 

190 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
125" 120" 115" 110" 105" 100° 

45" 

35" 

30" 

25" 

115" 110° 105" 100" 

95" eo• as· so· 

500 MILES --r--'-'-., ~,' -,---Ly.l,_.t___Jl 

500 KILOMETERS 

95" so· 85" 

75" 70" 65" 

45" 

40" 

35" 

30° 

25" 

so· 75" 

Figure 43.4. Locations of numbered geochemical studies (15-23, 26-29) of rocks, soils, and plants-the effects of 

pollution and relation to human and animal nutrition and disease. 

Tidball, R.R., 1975, Soils and plants in Kentucky, I and II (study 

nos. 18 and 19), in Connor, J.J., and Shacklette, H.T., 

Background geochemistry of some rocks, soils, plants, and 

vegetables in the conterminous United States: U.S. Geological Survey Professional Paper 574-F, p. F9. 

Study No. 13. Airborne Chemical Elements in Spanish 

Moss. 

Connor, J.J., and Shacklette, H.T., 1984, Factor analysis of the 

chemistry of Spanish moss: U.S. Geological Survey Professional Paper 574-I, 120 p. 

Shacklette, H.T., and Connor, J.J., 1973, Airborne chemical 

elements in Spanish moss: U.S. Geological Survey Professional Paper 574-E, 46 p. 

Study No. 14. Chemical Composition of Sedimentary 

Rocks, Alaska, Colorado, Idaho, Kansas, Montana, 

Nebraska, North Dakota, Oregon, South Dakota, 

Washington, and Wyoming. 

Hill, T.P., and Werner, M.A., 1972, Chemical composition of 

sedimentary rocks in Alaska, Idaho, Oregon, and Washington: U.S. Geological Survey Professional Paper 771, 

319 p. 

Hill, T.P., Werner, M.A., and Horton, M.J., 1967, Chemical 

composition of sedimentary rocks in Colorado, Kansas, 

Montana, Nebraska, North Dakota, South Dakota, and 

Wyoming: U.S. Geological Survey Professional Paper 561, 

241 p. 

III. GEOCHEMICAL STUDIES OF ROCKS, SOILS, 

AND PLANTS-EFFECTS OF POLLUTION AND 

RELATION TO HUMAN AND ANIMAL NUTRITION 

AND DISEASE (FIG. 43.4). 

Study No. 15. Helena, Montana-Copper Mines and 

Smelters. 

Miesch, A.T., and Huffman, Claude, Jr., 1972, Abundance and 

distribution of lead, zinc, cadmium, and arsenic in soils, 

chap. 4, in U.S. Environmental Protection Agency, Helena 

Valley, Montana area environmental pollution study: 

Research Triangle Park, N.C., Environmental Protection 

Agency, Office of Air Programs, 179 p. 

Bibliography of Selected Geochemical Studies of the Environment by the U.S. Geological Survey 191 
Study No. 16. Southeastern Idaho-Phosphate Mines 

and Mills. 

Gough, L.P., and Severson, R.C., 1976, Impact of point source 

emissions from phosphate processing on the element content of plants and soils, Soda Springs, Idaho, in Hemphill, 

D.O., ed., Trace substances in environmental health-X; 

Proceedings of University of Missouri's tenth annual conference on trace elements in environmental health, June 

8-10, 1976: Columbia, Mo., University of Missouri, p. 

225-233. 

Severson, R.C., and Gough. L.P., 1976, Concentration and 

distribution of elements in plants and soils near phosphate 

processing factories, Pocatello, Idaho: Journal of Environmental Quality, v. 5, no. 4, p. 476-482. 

---1979, Environmental implications of element emissions 

from phosphate-processing operations in southeastern 

Idaho: U.S. Geological Survey Professional Paper 1083, 

20 p. 

Study No. 17. Clay-Mine Spoil Related to Molybdenosis 

in Cattle. 

Case, A.A., Selby, L.A., Hutcheson, D.P., Ebens. R.J., Erdman, 

J.A., and Feder, G.L., 1973, Infertility and growth suppression in beef cattle associated with abnormalities in their 

geochemical environment, in HemphilL D.D., ed., Trace 

substances in environmental health-VI; Proceedings of 

University of Missouri's sixth annual conference on trace 

elements in environmental health. June 13-15, 1972: 

Columbia, Mo., University of Missouri, p. 15-21. 

Ebens, R.J., Erdman, J.A., Feder, G.L., Case, A.A .. and Selby, 

L.A., 1973, Geochemical anomalies of a claypit area, 

Callaway County, Mo., and related metabolic imbalance in 

beef cattle: U.S. Geological Survey Professional Paper 

807, 24 p. 

Erdman, J.A., 1978, Potential toxicology problems associated 

with strip mining, in Proceedings, Fourth Biennial Veterinary Toxicology Workshop, June, 1978: Logan, Utah State 

University, 11 p. 

Study No. 18. Geochemical Study of Soils and Plants in 

Areas of Georgia Having Contrasting Rates of Cardiovascular Diseases. 

Shacklette, H.T., 1975a, Garden soils. vegetables, native plants, 

and uncultivated soils in central and south-central Georgia 

(study no. 14), in Connor, J.J., and Shacklette, H.T., 

Background geochemistry of some rocks, soils, plants, and 

vegetables in the conterminous United States: U.S. Geological Survey Professional Paper 574-F, p. F8. 

---1975b, Garden soils, vegetables, native plants, and uncultivated soils in northern Georgia (study no. 15), in Connor, 

J.J., and Shacklette. H.T., Background geochemistry of 

some rocks, soils, plants, and vegetables in the conterminous United States: U.S. Geological Survey Professional 

Paper 574-F, p. F8. 

Shacklette, H.T., Sauer, H.I., and Miesch, A.T., 1970, Geochemical environments and cardiovascular mortality rates 

in Georgia: U.S. Geological Survey Professional Paper 

574-C, 39 p. 

---1972, Distribution of trace elements in the environment 

and the occurrence of heart disease in Georgia: Geological 

Society of America Special Paper 140, p. 65-70. 

Study No. 19. Effects of Mount St. Helens Ash Fall on 

the Chemistry of Fruits, Vegetables, and Associated 

Soils. 

Gough, L.P., Shacklette, H.T., Peard, J.L., and Papp, C.S.E., 

1986, The chemistry of fruits and vegetables, Yakima 

River Valley, Washington, and the influence of the 1980 

Mount St. Helens ash fall episodes: U.S. Geological 

Survey Bulletin 1640, 13 p. 

Study No. 20. Effects of Mount St. Helens Ash Fall on 

the Chemistry of Soils and Wheat, and Ash Leachate 

Chemistry. 

Gough, L.P., Severson, R.C., Lichte, F.E., Peard, J.L., Tuttle, 

M.L., Papp, C.S.E., Harms, T.F., and Smith, K.S., 1981, 

Ash fall effects on the chemistry of wheat and the Ritzville 

soil series, eastern Washington, in Lipman, P. W., and 

Mullineaux, D.R., eds., The 1980 eruptions of Mount St. 

Helens, Washington: U.S. Geological Survey Professional 

Paper 1250, p. 761-782. 

Hinkley, T.K., and Smith, K.S., 1987, Leachate chemistry of ash 

from the May 18, 1980 eruption of Mount St. Helens, part 

B a/Chemistry of ash and leachates from the May 18, 1980 

eruption of Mount St. Helens, Washington: U.S. Geological Survey Professional Paper 1397. p. 23-64. 

Hinkley, T.K., Smith, K.S., Taggart, J.E., Jr., and Brown, J.T., 

198 7, Chemical and mineralogical aspects of observed 

fractionation of ash from the May 18, 1980 eruption of 

Mount St. Helens, part A a/Chemistry of ash and leachates 

from the May 18, 1980 eruption of Mount St. Helens, 

Washington: U.S. Geological Survey Professional Paper 

1397' p. 1-22. 

Study No. 21. Front Range Urban Corridor, 

Colorado-Elements in Soils. 

Tourtelot, H.A., 1973, Regional geochemical investigations, 

Front Range Urban Corridor, Colorado [abs.]: Geological 

Society of America, Abstracts with Programs, v. 5, no. 6, 

p. 520-521. 

---1975. Surficial materials, Longmont, Colorado, area, in 

Connor, J. J .. and Shacklette, H. T., Background geochemistry of some rocks, soils, plants, and vegetables in the 

conterminous United States: U.S. Geological Survey Professional Paper 574-F, p. F9-F10. 

192 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry 
Study No. 22. Chemistry of Fruits and Vegetables and 

Associated Soils from Areas of Commercial Production 

in the United States. 

Boerngen. J.G .. and Shacklette, H.T., 1980, Chemical analyses 

of fruits, vegetables, and their associated soils from areas of 

commercial production in the contern1inous United States: 

U.S. Geological Survey Open-File Report 80-84, 135 p. 

Shacklette, H.T., 1980, Elements in fruits and vegetables from 

areas of commercial production in the conterminous United 

States: U.S. Geological Survey Professional Paper 1178, 

149 p. 

Study No. 23. Effects of Mine Spoil on the Chemistry of 

Soils and Plants. 

Ebens, R.J., and Erdman, J.A., 1982, Sweetclover and associated 

spoil materials from selected coal mines in the northern 

Great Plains (study no. 10), in Ebens. R.J .. and Shacklette, 

H.T., Geochemistry of some rocks, mine spoils, stream 

sediments, soils, plants, and waters in the western energy 

region of the conterminous United States: U.S. Geological 

Survey Professional Paper 1237, p. 11-13. 

Erdman, J.A., and Ebens, R.J., 1982, Crested wheatgrass at the 

Dave Johnston mine (study no. 26), in Ebens, R.J., and 

Shacklette, H.T., Geochemistry of some rocks, mine 

spoils, stream sediments, soils, plants, and waters in the 

western energy region of the conterminous United States: 

U.S. Geological Survey Professional Paper 1237, p. 

21-24. 

Gough, L.P., and Severson, R.C., 1982, Soils, mine spoils, and 

native plants at the San Juan Mine, New Mexico (study no. 

11 ). in Ebens, R.J .. and Shacklette, H. T., Geochemistry of 

some rocks, mine spoils, stream sediments, soils, plants, 

and waters in the western energy region of the conterminous United States: U.S. Geological Survey Professional 

Paper 1237, p. 12-13. 

Severson, R.C., and Gough. L.P., 1981, Chemical character of 

minesoils at one Alaskan and twelve western conterminous 

United States coal-stripmines: U.S. Geological Survey 

Open-File Report 81-243, 82 p. 

---1983a, Rehabilitation materials from surface-coal mines in 

Western U.S.A., pt. I, Chemical characteristics of spoil 

and replaced cover-soil: Reclamation and Revegetation 

Research, v. 2, p. 83-102. 

----1983b, Boron in mine soils and rehabilitation plant 

species at selected surface-coal mines in Western United 

States: Journal of Environmental Quality, v. 12, 

p. 142-146. 

Study No. 24. Molybdenosis in Cattle, Northern Great 

Plains. 

Erdman, J.A .. Ebens, R.J., and Case, A.A., 1978, Molybdenosis-A potential problem in ruminants grazing on coal mine 

spoils: Journal of Range Management, v. 31, no. 1, 

p. 34-36. 

Stone, L.R., Erdman, J.A., Feder. G.L., and Holland, H.D., 

1983, Molybdenosis in an area underlain by uraniumbearing lignites in the northern Great Plains: Journal of 

Range Management, v. 36, no. 3, p. 280-285. 

Study No. 25. Plant, Soil, and Rock Chemistry, Capps 

Coal Field, Alaska. 

Gough, L.P., and Severson, R.C., 1981, Element concentrations 

in rehabilitation species from thirteen coal-strip mines in 

the five Western States and Alaska: U.S. Geological 

Survey Open-File Report 81-182, 118 p. 

---1983. Chemical analyses of native soil and vegetation 

samples, Capps coal field, Alaska: U.S. Geological Survey 

Open-File Report 83-246, 58 p. 

Gough, L.P., Severson, R.C., and Briggs, P.H., 1982, Field 

observations and chemical analyses of vegetation, soils, 

and spoil materials, Jarvis Creek preference coal lease, 

Alaska: U.S. Geological Survey Open-File Report 82-55, 

33 p. 

---1984, The distribution and mobility of elements in soils 

and plants, Capps coal field, Alaska [abs.]: Geological 

Society of America Abstracts with Programs, v. 16, no. 5, 

p. 287. 

Hinkley, T.K., Smith. K.S., Peard, J.L., and Tompkins, M.L., 

1982, Whole-rock chemical composition of some samples 

from two drill hole cores in the Capps coal field, Beluga 

coal area. south-central Alaska: U.S. Geological Survey 

Open-File Report 82-672, 58 p. 

Severson, R.C., and Gough, L.P., 1983, Chemical composition 

and variability of soils from the Capps coal field, Alaska: 

U.S. Geological Survey Open-File Report 83-190, 39 p. 

Study No. 26. Element Composition of Small Grains, 

South Dakota. 

Erdman, J.A., and Moul, R.C., 1982, Mineral composition of 

small-grain cultivars from a uniform test plot in South 

Dakota: Journal of Agricultural and Food Chemistry, v. 30, 

p. 169-174. 

Study No. 27. Soil Chemistry Related to Human Mortality and Swine Birth Defects, Missouri. 

Selby, L.A., and Tidball, R.R., 1976, The environmental geochemistry of agricultural soils in Missouri and its association with swine birth defects, in Hemphill, D.D., ed., 

Trace substances in environmental health-X; Proceedings 

of University of Missouri's tenth annual conference on 

trace substances in environmental health: Columbia, Mo., 

University of Missouri, p. 63-70. 

Tidball,,R.R .. and Sauer, H.I.. 1975, Multivariate relationships 

between soil composition and human mortality rates in 

Missouri, in Trace element geochemistry in health and 

disease: Geological Society of America Special Paper 155, 

p. 41-59. 

Bibliography of Selected Geochemical Studies of the Environment by the U.S. Geological Survey 193 
Study No. 28. Soil and Plant Chemistry, Four Corners 

Powerplant. 

Cannon, H.L., and Anderson, B.M., 1972, Trace element content 

of the soils and vegetation of the Four Comers Power Plant, 

pt. III, Report of the coal resources work group, Southwest 

Energy Study: U.S. Department of the Interior, Administrative Report, 44 p. 

Connor, J.J., Anderson, B.M., Keith, J.R., and Boemgen, J.G., 

1976, Soil and grass chemistry near the Four Comers 

Powerplant, in Geochemical survey of the western coal 

regions, 3d annual progress report, July 1976: U.S. Geological Survey Open-File Report 76-729, p. 112-120. 

Study No. 29. Elements in Vegetables and Field Corn in 

the Lead-Zinc District, Wisconsin. 

Shacklette, H.T., 1975, Garden vegetables and field com in 

Wisconsin, Minnesota, and Iowa, in Connor, J .J., and 

Shacklette, H.T., Background geochemistry of some rocks, 

soils, plants, and vegetables in the conterminous United 

States: U.S. Geological Survey Professional Paper 574-F, 

p. FlO. 

Study No. 30. U.S. Geological Survey-National Parks 

Service Cooperative Studies in Environmental Biogeochemistry. 

Gough, L.P., Jackson, L.L., and Bennett. J.P., 1986, The 

assessment of airborne sulfur and trace-metal contamination in National Parks-Cooperative studies between the 

USGS and NPS [abs.], in Conference on Science in the 

National Parks, Programs and abstracts, July 13-18, 1986: 

National Park Service Publication, p. 157. 

Gough, L.P., Jackson, L.L., Bennett, J.P., Severson, R.C., 

Engleman, E.E., Briggs, P.H., and Wilcox, J.R., 1986, 

The regional influence of an oil-fired power plant in the 

concentration of elements in native materials in and near 

south Florida national parks: U.S. Geological Survey 

Open-File Report 86-395, 63 p. 

Gough, L.P., Jackson, L.L.. Severson, R.C., and Bennett, J.P., 

1985, Sources of sulfur and trace metals near Everglades 

Park and adjacent agricultural lands of southern Florida, 

U.S.A., in Kabata-Pendias, Alina, ed., Proceedings, 

National Conference on Effects of Trace Pollutants on 

Agricultural Environmental Quality, 3d. May 28-30, 1985, 

Pulawy, Poland, v. 1 [in Polish]: Pulawy, Poland, Polish 

Institute of Soil Science and Plant Cultivation, p. 85-89. 

Study No. 31. Vegetation Zonation and Metal Stress. 

Gough, L.P., 1986, Vegetation zonation, metal stress, and mineral exploration, in Rubey, W.W., Organic matter, biological systems and mineral exploration: Englewood Cliffs, 

N.J., Prentice-Hall, v. 5, p. 33-46. 

Study No. 32. Geochemical Studies in Hawaii. 

Connor, J.J., 1979, Geochemistry of ohia and soil lichen, Puhimau thermal area, Hawaii: The Science of the Total 

Environment, v. 12, no. 3, p. 241-250. 

Study No. 33. Studies of the Belt Supergroup Rocks, 

Montana. 

Connor, J.J., 1984, Geochemistry of the middle Proterozoic, 

Spokane, Grinnell, and St. Regis Formations of the Belt 

Supergroup, in The Belt, abstracts and summaries, Belt 

Symposium II, 1983: Montana Bureau of Mines and 

Geology Special Publication 90, p. 102-103. 

Study No. 34. Geochemistry of Combustion of Coal. 

Connor, J.J., 1977, Trace element emissions, Dave Johnston 

Powerplant, Wyoming, in Geochemical survey of the 

western energy regions, fourth annual progress report, July 

1977: U.S. Geological Survey Open-File Report 77-872, 

p. 65-76. 

Herring, J.R., 1980, C02 and volatile trace element emissions to 

the atmosphere from naturally burning coal [abs.]: Eos 

(Transactions, American Geophysical Union), v. 61, 

p. 967. 

Herring, J.R., and Rick, F.J., 1983, Spontaneous coal combustion; mechanisms and prediction, in Proceedings, International Conference on Coal Science, 1983: Pittsburg, Pa., 

International Energy Agency, p. 753-756. 

Study No. 35. Acid Rain. 

Herring, J.R., 1984, Acid rain research in the Geologic Division, 

U.S. Geological Survey: Administrative report prepared for 

Geologic Division, U.S. Geological Survey Coordinator on 

Acid Rain Research, 9 p. 

Study No. 36. Baseline Values for Uranium and Thorium in Soils and Sediments. 

Shacklette, H.T., Gough, L.P., and Severson, R.C., 1986, 

Baseline values for uranium and thorium in soils and other 

unconsolidated sediments and in stream and lake sediments: 

U.S. Geological Survey Administrative Report, 14 p. 

Study No. 37. Element Concentrations Toxic to Plants, 

Animals, and Man. 

Gough, L.P., Shacklette, H.T., and Case, A.A., 1979, Element 

concentrations toxic to plants, animals, and man: U.S. 

Geological Survey Bulletin 1466, 80 p. [reprinted]. 

194 Proceedings of a U.S. Geological Survey Workshop on Environmental Geochemistry